Liquid crystalline polymer compositions, process, and products

ABSTRACT

Novel compositions comprising a high concentration of one or more extended chain homopolymer, copolymer, or block polymer and certain polyphosphoric acids are prepared. Such compositions are optically anisotropic (liquid crystalline), capable of exhibiting excellent cohesive strength, and are especially suited to the production of high molecular weight ordered polymer fibers by dry-jet wet spinning. These liquid crystalline compositions are capable of being drawn through long air gap distances and spun at exceptionally high spin draw ratios. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

ORIGIN OF INVENTION

This invention was made with Government support under U.S. Department ofDefense contract Nos. F33615-81-K-5070, F49620-81-K-0003, and/orF33615-82-C-5079 awarded by the United States Air Force. The Governmenthas certain rights in this invention.

TECHNICAL FIELD OF INVENTION

The present invention relates broadly to novel anisotropicliquid-crystalline extended chain polymerpolyphosphoric acidcompositions, to the production of high molecular weight extended chainpolymers by polycondensation of selected monomers in certainpolyphosphoric acids, and especially to the production of highlyconcentrated polymer compositions from which industrially usefulpolymeric articles such as fibers and films are readily produced.

Among some of the most serious difficulties encountered in theproduction of thermally stable articles such as fibers and films fromextended chain polymers are described in the Background Art below.

BACKGROUND OF INVENTION

1. Reference to Related Applications

Reference is made to another United States patent application filedconcurrently with the present application, both being assigned to SRIInternational and having as one of their inventors, James F. Wolfe. Saidother application is entitled: "Liquid CrystallinePoly(2,6-benzothiazole) Compositions, Process, and Products" and isherein incorporated by reference.

2. Background Art

In general, the class of aromatic heterocyclic extended chain polymersare well known for their outstanding thermal, physical, and chemicalproperties. Unfortunately, these polymers are essentially non-meltingand have proven very difficult to economically process into articles. Inorder to fashion such polymers into desired articles of commerce, forexample fibers, films, fibrids, and the like, it is necessary that theybe in solution or dope form. Although such polymers can be dissolved invarious acidic solvents, such as sulfuric acid, methanesulfonic acid,chlorosulfonic acid, polyphosphoric acid, and the like, difficulty isoften experienced in preparing and using the polymer-acid compositionsor dopes because of poor polymer-acid solubility.

Normally, a precipitated or dried particulate form of the polymer isdissolved in a strong acidic solvent by mixing the (isolated) polymerparticles at elevated temperatures and/or under high pressures for aperiod from several hours to several days. If the polymer is insolublein the particular solvent, other solvents or various solvent mixturesare employed. Usually, heating and cooling cycles are applied andrepeated to obtain a useful dope.

The resulting dopes often contain undissolved polymer and must befiltered before further processing into articles.

Although spinning dopes of polybenzobisoxazole, polybenzimidazole andpolybenzobisthiazole in sulfuric acid and/or methanesulfonic acid and/orchlorosulfonic acid with polymer concentrations above about 10 percentare known in the art, the intrinsic viscosity of these polymers is forthe most part below 5dL/g and oftentimes less than 3dL/g. The cohesivestrength of such dopes is inherently weak and economically lessdesirable for use in dry-jet wet spinning. In the case ofpolybenzobisoxazole, numerous attempts of dry-jet wet spinning anapproximately 10% polybenzobisoxazole/methane sulfonic acid-dope intofibers were not successful (E. W. Choe, et al., in Macromolecules 1981,14, pp. 920-924).

In the case of polybenzimidazole, prior art dopes of this polymer lackadequate strength to maintain filament integrity while dropping throughthe air-gap. In order to overcome this problem U.S. Pat. No. 4,263,245teaches dissolving a high concentration (up to 30%) of this polymer intosuitable solvents such as concentrated sulfuric acid. At such highpolymer concentrations lithium chloride is required to prevent thepolybenzimidazole from phasing out of solution.

In the case of polybenzobisthiazole, U.S. Pat. No. 4,225,700 teaches theformation of a liquid crystalline composition of this polymer atconcentrations near 10% in methane sulfonic acid and chlorosulfonic acidand at about 6% in polyphosphoric acid. Concentrations ofpolybenzobisthiazole in polyphosphoric acid above about 10% by weightare difficult, if indeed possible to achieve. One difficulty encounteredis that the solution of the 2,5-diamino-1,4-benzenedithiol monomer inpolyphosphoric acid with the P₂ O₅ content described in U.S. Pat. No.4,225,700 is very viscous and dehydrohalogenation is difficult. Alsoconsiderable foaming results. Although solutions of precipitated polymerin solvents such as methane sulfonic acid and chlorosulfonic acid can beprepared, high concentrations of polymer are difficult or impossible toachieve. S. R. Allen, et al., in Macromolecules 1981, 14, pp. 1135-1139describes attempts at spinning polybenzobisthiazole directly from thepolymerization medium (polyphosphoric acid) containing 5-6% polymer.

Insofar as polybenzobisthiazole is concerned it is possible to obtaincompositions near to 10% of the polymer in polyphosphoric acid withintrinsic viscosity equal to 26dL/g (J. F. Wolfe, et al., Macromolecules1981, 14, pp. 915-920). Attempts to increase the intrinsic viscosity ofthe polymer can only be achieved at a major sacrifice (decrease) inpolymer concentration. Liquid crystalline compositions of 10%polybenzobisthiazole in polyphosphoric acid are heretofore unknown inthe art. Liquid crystalline compositions of polybenzobisthiazole havingintrinsic viscosities greater than about 30.3dL/g in polyphosphoric acidare heretofore unknown in the art.

In practical terms this means that such polymerpolyphosphoric acidcompositions are severely limited in their potential usefulness for theproduction of highly ordered high molecular weight polymeric articles.

In general, liquid crystalline extended chain polymer compositions (withthe exception of polybenzobisthiazole as mentioned above) inpolyphosphoric acid are heretofore unknown in the art; and moreover,liquid crystalline extended chain copolymer and block polymercompositions are heretofore unknown in the art.

DISCLOSURE OF INVENTION

1. Objects of Invention

Accordingly, it is an object of the present invention to providecompositions substantially free of one or more of the disadvantages ofprior art compositions.

Another object is to provide a process for preparing liquid crystallineextended chain polymer compositions.

A further object is to provide liquid crystalline extended chain polymercompositions having excellent cohesive strength.

Another object is to provide liquid crystalline extended chain polymercompositions having excellent spin stretchability.

Another object is to provide liquid crystalline extended chain polymercompositions capable of being drawn through long air gap distances.

Yet another object is to provide liquid crystalline extended chainpolymer compositions capable of being drawn at high spin draw ratios.

A further object of the invention is to prepare a liquid crystallinespinning composition having a high extended chain polymer content.

A still further object is to provide liquid crystalline extended chainhomopolymer compositions.

Another object is to provide liquid crystalline extended chain copolymercompositions.

Yet another object is to provide liquid crystalline extended chain blockpolymer compositions.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain homopolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain copolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain block polymer.

Another object of the invention is to provide a method of preparingliquid crystalline extended chain polymer compositions from selectedmonomers.

Another object is to provide a process for preparing liquid crystallinehigh molecular weight extended chain polymer compositions.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain homopolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain copolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain block polymers.

A still further object is to provide a method whereby thedehydrohalogenation of certain hydrohalide monomers may be carried outmore easily and rapidly.

Yet another object is to provide a method whereby a substantially higherconcentration of monomeric reactants can be employed which results inliquid crystalline extended chain polymer compositions of considerablyhigher polymer concentration than has been possible heretofore.

Another object is to alleviate the foaming problem referred to above.

Another object is to provide articles prepared from liquid crystallineextended chain polymer compositions.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain homopolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain copolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain block polymers.

The above and other objects of the invention will be apparent from theensuing description and the appended claims.

2. Statement of Invention

In accordance with our discovery, the present invention broadlyencompasses novel polymer compositions which are useful as dopes in theproduction of high strength shaped articles comprising blends of certainpolyphosphoric acids, as described hereinafter, and a high concentrationof one or more high molecular weight extended chain polymers having oneor more mesogenic group or groups. The extended chain polymers can behomopolymers, copolymers, or block polymers, as exemplified hereinafter.The extended chain polymer is present in the blend at a sufficientconcentration so as to be capable of exhibiting an anisotropic polymerphase alone or in combination with one or more different polymers withor without mesogenic group or groups. The blends according to theinvention are polycondensation products obtained by reaction of selectedmonomers in an appropriate solution of phosphoric acid, as describedhereinafter. These blends exhibit special properties which make themvery useful as dopes in the production of fibers, films, fibrids, andthe like. In addition to being anisotropic (liquid-crystalline), theblends have a novel combination of properties including unexpectedlyhigh spin-stretchability and excellent cohesive strength, as well ashaving the capability of being drawn through short, as well as extremelylong, air-gap distances, and spun at low, as well as exceptionally high,draw ratios. It is believed that these properties can be attributed tothe combination of high polymer concentration, high polymer molecularweight, and a high phosphorus pentoxide content comprising the blends ofthe present invention.

Our discovery further broadly encompasses a process for preparing novelextended chain polymer compositions which are useful as dopes in theproduction of fibers and films. This process comprises:

(a) mixing at least one of a selected first monomer (as describedhereinafter) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a first mixture of the first monomer in the preliminarysolvent,

(c) adding at least one of a selected second monomer (as describedhereinafter) in the resulting mixture of step (b) to provide a firstmixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (c) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(e) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product or a first cooligomeric product having apreselected intrinsic viscosity, or

(f) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomopolymeric product or a first copolymeric product,

(g) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, the secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1g) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (1g) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(3g) causing polymerization of the first or first and second monomer ata temperature sufficient to effect reaction at a rate to form the secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomers ofstep (a) or (1g) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomers of step (a) or (c)which forms the first homo-oligomeric product, or

(h) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of at least one of a selected firstmonomers or a first and second monomer in the preliminary solvent so asto form a monomer-oligomer mixture, and then increasing the phosphoruspentoxide content of the monomer-oligomer mixture to provide amonomer-oligomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization, the first monomer of the second mixturebeing formed by like steps (a) and (b) and the first and second monomerof the second mixture being formed by like steps (a), (b) and (c), withthe overall proviso that at least one of the selected monomers of step(a) or (c) which forms the first or first and second monomer of thesecond mixture, be different from at least one of the selected monomersof step (a) or (c) which forms the first homo-oligomeric product.

(i) causing polymerization of the polyoligomeric product resulting fromstep (g) or the monomer-oligomer resulting from step (h) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

3. Mode(s) for Carrying Out the Invention

The extended chain polymers of the compositions of the present inventionare a class of polymers that can obtain a substantial degree of shapeanisotropy in the liquid state due to restricted rotation of bonds inthe polymer backbone and/or appropriate catenation geometry of rigidbackbone segments. The degree of shape anisotropy is generally definedby the axial ratio, (ρ)/d, where (ρ) is the persistence length of thechain and d is the diameter of the chain. For extended chain polymers,(ρ) may be substantially the same as or greater than the contour length1 of the polymer. In the case of a rigid rod polymer, (ρ) is essentiallyinfinite and the axial ratio is 1/d.

By the method of the present invention, it is possible to prepare liquidcrystalline compositions of extended chain homopolymers, copolymers, orblock polymers containing 15 percent or more of polymer. As will appear,the invention is applicable to the preparation of liquid crystallineextended chain polymer compositions of lower polymer concentration butthere are special advantages to preparing compositions of highconcentration.

Extended chain polymer-polyphosphoric acid compositions of such higherpolymer concentration are advantageous. For example, if the polymer isone, such as polybenzobisthiazole, polybenzobisoxazole, andpolybenzobisimidazole, capable of forming liquid crystallinecompositions at low concentration (e.g., 5-10%), that is, if thecritical concentration necessary for formation of the anisotropic phaseis low, compositions of even higher polymer concentration can be spun toproduce a better quality, higher strength fiber. We believe thisresults, in part at least, from a more fully anisotropic composition andimproved composition integrity. These improvements allow greater drawingin the air-gap, improve the coagulation characteristics, which leads tofewer flaws, and increase polymer throughput when a liquid crystallinecomposition is spun by a dry-jet-wet spinning technique into apolyphosphoric acid-solvent/polymer-nonsolvent such as methanol, water,or dilute aqueous acid(s).

If the polymer is one, such as poly (2,6-benzothiazole) that is lessrodlike in structure than polybenzobisthiazole or polybenzobisoxazoleand thus possesses a critical concentration for anisotropic phaseformation greater than 10% and in the region of concentrations of thisinvention, extruding of these heretofore unattainable solutions producesa dramatic increase in strength and modulus because of the ordering ofthe polymer during fabrication.

These advantages result in a more highly ordered, lower-defect fiberthan results from spinning a less concentrated composition of polymers.

Another advantage of preparation of these polymers in the anisotropicphase is a considerable increase in the molecular weight of the polymerobtained.

Preliminarily it is helpful to describe the chemistry of phosphoricacids and strong phosphoric acids or polyphosphoric acids as follows:

As used herein the term "phosphoric acid(s)" means commercial phosphoricacid(s) containing 85-86% H₃ PO₄.

The strong phosphoric acids, or polyphosphoric acids referred to as ppa(polyphosphoric acid) are members of a continuous series of amorphouscondensed phosphoric acid mixtures given by the formula

    H.sub.n+2 P.sub.n O.sub.3n+1

or

    HO--PO.sub.3 H.sub.n H

where the value of n depends on the molar ratio of water to phosphoruspentoxide present.

Characterization and methods of forming various polyphosphoric acids andexamples of such strong acids useful in accordance with the practice ofthe present invention can be found in the following papers: A. L. Huhtiand P. A. Gartaganis "The Composition of the Strong Phosphoric Acids,"Can. J. Chem., Vol. 34, 1956 pp. 785-797; and J. E. Such, "LinearPolyphosphoric Acids", Mellar's Comprehensive Treatise on Inorganic andTheoretical Chemistry, Vol. VIII, Supplement III, pp. 726-753, Wiley1971. The subject matter of these articles are specifically incorporatedherein by reference.

In its most general definition, polyphosphoric acid composition canrange from distributions where the average value of n is less thanunity, giving rise to a mobile liquid, to high values of n, where thepolyphosphoric acid is a glass at normal temperatures. Because thespecies of polyphosphoric acid are in a mobile equilibrium, a givenequilibrium composition can be prepared in many ways. For instance, thesame distribution or polyphosphoric acid composition could be preparedby either starting with concentrated orthophosphoric acid (H₃ PO₄, n=1)and driving off water or by starting with phosphorus pentoxide (P₂ O₅)and adding an appropriate amount of water.

All polyphosphoric acid compositions can be described as a ratio of P₂O₅ and water by reducing the various species present (on paper) to P₂ O₅and water. We will then use the convention that polyphosphoric acidcomposition will be expressed in terms of a P₂ O₅ content (as apercentage) defined as P₂ O₅ content ##EQU1## Thus, the P₂ O₅ content ofpure orthophosphoric acid could be derived by reducing one mole of H₃PO₄ to 0.5 moles P₂ O₅ +1.5 moles H₂ O. Converting to weights gives theP₂ O₅ content as ##EQU2##

Similarly, the P₂ O₅ content of commercial polyphosphoric acid can bederived in the following way. Polyphosphoric acid is availablecommercially in two grades, 105% and 115%. These percentages refer to H₃PO₄ content, which means that 100 g of the two grades contain 105 and115 grams of H₃ PO₄. The P₂ O₅ content of 115% polyphosphoric acid canthen be calculated knowing the P₂ O₅ content of 100% H₃ PO₄. ##EQU3##Freshly prepared polyphosphoric acid as described by Wolfe and Loo U.S.Pat. 4,225,700 employed 1.52×g of P₂ O₅ to ×grams of 85.6% H₃ PO₄, thusthe P₂ O₅ content of that mixture is ##EQU4##

Thus, polyphosphoric acid compositions, by our definition, equivalent tothese three examples could be prepared in principle by starting with P₂O₅ and adding 27.6, 16.7, and 15.1% by weight of water.

Homopolymeric Compositions and their preparation

In accordance with one aspect of the invention, there is provided aliquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain homopolymer having thegeneral formulas: ##STR1## wherein Ar¹ represents an aromatic moiety andis XX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or represents a bivalent organic radical and isXXI as defined below, n being a positive integer; ##STR2## wherein Ar³represents an aromatic moiety and is XXII as defined below, X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₃ being bonded to aromatic carbon atoms of Ar³, Nand X₃ of each hetero ring are disposed ortho to one another, n being apositive integer; ##STR3## wherein Ar¹ represents an aromatic moiety andis XX as defined below, and Ar⁴ represents an aromatic moiety and isXXIII as defined below, the nitrogen atoms being bonded to aromaticcarbon atoms of Ar¹ and the carbon atoms being bonded to aromatic carbonatoms of Ar⁴, n being a positive integer; ##STR4## wherein Ar⁵represents an aromatic moiety and is XXIV as defined below, the nitrogenatoms being bonded to Ar⁵, n being a positive integer; ##STR5## whereinAr⁶ represents an aromatic moiety and is XXV as defined below, Ar¹represents a different aromatic moiety and is XX as defined below, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, n being a positive integer;##STR6## wherein Ar⁹ represents an aromatic moiety and is XXVI asdefined below, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁹, n being a positive integer; ##STR7## wherein Ar¹represents an aromatic moiety and is XXVII as defined below, Y⁷represents an aromatic moiety and is XXVIII as defined below, thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer; ##STR8##wherein Ar¹ represents an aromtic moiety and is XX as defined below, Y⁸is XXIX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹ and adjacent carbon atoms of Y⁸, N and X₁ or X₂ of each hetero ringare disposed ortho to one another, n being a positive integer.

The aromatic moieties Ar¹, Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁹, and Y², Y⁷, and Y⁸of the extended chain polymer formulas above are defined as follows:##STR9## Any monomeric material or mixture of monomeric materials havingthe ability to react in polyphosphoric acid to form the extended chainpolymers (i.e., the above formulas I-VIII homopolymers, and the variousformulas IX-XIX copolymers and block polymers herein defined in thespecification) of this invention can be utilized.

In general, suitable monomeric materials selected for use in formingliquid-crystalline extended chain polymer compositions of the presentinvention are of nine types as described below.

Type 1 monomers have the general formula ##STR10## wherein Ar¹ is anaromatic moiety; X₁ and X₂ are the same or different atoms or groupsselected from the class O, S, and NR; R is hydrogen or an organic groupattached to N; the R's on the two nitrogen atoms where both X₁ and X₂are NR may be the same or different; NH₂, X₁ H and X₂ H are bonded toaromatic carbon atoms of Ar¹ ; the groups on the left side of Ar¹ areortho with respect to one another and the groups on the right side ofAr¹ are ortho with respect to one another.

The two sets of NH₂ and XH are positioned on Ar¹ such that they do notboth interact partially with the appropriate condensing moiety ofanother monomer. Monomer 1 is typically isolated as a hydrohalide saltof the monomer.

In general, Ar¹ may be any aromatic moiety (carbocyclic or heterocyclic)and it may be a single ring such as ##STR11## or it may comprise aplurality of aromatic rings connected by valence bonds or by linkingatoms or groups such as ##STR12## where β is a valence bond (as indiphenyl) or a divalent atom (--O-- or --S--) or group such as--NR--(R=H or an organic group), --(CH₂)_(n) -- (n=1 or a higherinteger). Specific examples of Ar¹ are as follows: ##STR13## Thearomatic ring or rings of Ar¹, such as those described above and others,may bear one or more substituent. These substituents, which may beorganic or inorganic may be or may contain hetero atoms, may be any atomor group which is compatible with the reactant, the solvent, thepolycondensation reaction and the resulting oligomer or polymer.Substituents which are chemically reactive with types 2 thru 9 monomers(see below), with the solvent (PPA) or with the oligomeric or polymericproducts are to be avoided. Also, substituents which offer sterichindrance to the polycondensation are to be avoided.

Among permissible hydrocarbon substituents are alkyl (e.g., C₁ to C₁₀straight chain and branched chain alkyl, benzyl, etc.), phenyl chlorosubstituted alkyl, phenyl and benzyl. Among permissible heterosubstituents are chloro, bromo, nitro, alkoxy, aryloxy, SO₃ H, and --OR,SR, and --NR₁ R₂ (R₁ and R₂ being organic groups).

Formula 1 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (1,1), Class 2 (1,2),and Class 3 (1,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (1,1) monomers are those wherein Ar¹ is a six-memberedaromatic ring with the four valence positions being on carbon atomshaving a 1, 2, 4, 5 relationship to each other, such as 1, 2, 4,5-benzene or 2, 3, 5, 6-pyridine; R is H or a monovalent aromaticradical, such as phenyl, or a monovalent heteroaromatic radical, such as2-pyridyl, or a monovalent aliphatic radical, such as methyl. Monomers(1,1) which when reacted with a diacid or a diacid derivative give twosubstantially collinear bonds are most preferred.

Specific examples of (1,1) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 1 below.

                  TABLE 1                                                         ______________________________________                                        Monomers of Type 1, Class 1                                                   ______________________________________                                         ##STR14##                                                                    2,5-diamino-1,4-benzenedithiol dihydrochloride                                obtained according to Wolfe, et. al.,                                         Macromolecules, Vol. 14, Page 915 (1981).                                      ##STR15##                                                                    4,6-diamino-1,3-benzenediol dihydrochloride                                   obtained from 4,6-dinitro-1,3-benzenediol                                     according to Wolfe, et al., Macromolecules, Vol.                              14, Page 909 (1981).                                                           ##STR16##                                                                    1,2,4,5-tetraaminobenzene tetrahydrochloride                                  obtained from Aldrich Chemical Co. and purified                               by recrystallization from dilute HCl by heating,                              adding charcoal, filtering, and adding                                        concentrated HCl.                                                              ##STR17##                                                                    2,5-diamino-1,4-benzenediol dihydrochloride                                   prepared according to Wolf, et. al., J. Polymer                               Sci., Part A-1, Vol. 6, page 1503 (1968).                                      ##STR18##                                                                    2,3,5,6-tetraaminopyridine trihydrochloride                                   prepared by the dinitration of 2,6-diamino                                    pyridine, followed by hydrolysis and reduction by                             the method of A. H. Gerber, J. Polymer Sci.,                                  Polymer Chemistry Ed., Vol. 11, page 1703(1973).                               ##STR19##                                                                    3,5-diamino-2,6-pyridinediol trihydrochloride                                 prepared by dinitration of 2,6-dimethoxy pyridine                             according to C. D. Johnson, et al., J. Chem. Soc.                             (B), 1967, page 1204, followed by reduction and                               dealkylation.                                                                  ##STR20##                                                                    3,6-diamino-2,5-pyridinedithiol dihydrochloride                               prepared from commercially available 2,5-                                     diamino-pyridine by methods analogous to the                                  preparation of 1a.                                                             ##STR21##                                                                    N.sup.1,N.sup.5diphenyl-1,2,4,5-tetraaminobenzene dihydrochloride             prepared starting from m-dichlorobenzene                                      according to H. Vogel and C. S. Marvel, J.                                    Polym. Sci., A, Vol. 1, page 1531 (1963) and                                  purified from toluene before use.                                             ______________________________________                                    

The preferred (1.2) monomers are those wherein Ar¹ is two six-memberedaromatic rings attached by a covalent carbon-carbon bond each withvalences on carbon atoms in the 3 to 4 positions, such as3,3',4,4'-biphenyl or 4,4', 5,5'-(2,2'-bipyridyl), or Ar¹ is two fusedsix-membered rings with valence positions being on carbon atoms andhaving a 1,2,5,6 relationship to each other, such as1,2,5,6-naphthalene.

The four functional groups attached to the valence positions of Ar¹ bycovalent bonds comprise two amino groups and the groups --X₁ H and --X₂H such that one amino group is ortho to --X₁ H and the other amino groupis ortho to X₂ H and X₁ H is attached to either the 3 or 4 position inthe first case or the 1 or 2 position in the second case and --X₂ H isattached to either the 3' or 4' position in the first case and the 5 or6 position in the second case. X₁ and X₂ are defined as above.

Specific examples of (1,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Monomers of Type 1, Class 2                                                   ______________________________________                                         ##STR22##                                                                    1i                                                                            3,3'-dimercaptobenzidine dihydrochloride                                      prepared by the method of Houben-Weyl, Methoden                               der Organischen Chemie, E. Miller, Ed., Vol IX, page 39 (1955).                ##STR23##                                                                    1j                                                                            3,3'-dihydroxybenzidine dihydrochloride                                       prepared by the method of C. G. Vogt and F.                                   Marschall, U.S. Pat. No. 2,497,248 (1950) from                                o-dianisidine and aluminum chloride.                                           ##STR24##                                                                    1k                                                                            3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride                           prepared by the method of Y. Imai, I. Taoka, K.                               Uno, and Y. Iwakura, Makromol. Chem, 83, page 167 (1965).                      ##STR25##                                                                    1l                                                                            3,3'-diaminobenzidine tetrahydrochloride dihydrate                            prepared according to (same ref. as for 1h) and                               the tetrahydrochloride recrystallized from dilute                             HCl containing stannous chloride by adding                                    concentrated HCl.                                                              ##STR26##                                                                    1m                                                                            3,3'-diamino-4,4'-dianilinobiphenyl dihydrochloride                           prepared from dinitration of 4,4'-                                            dichlorobiphenyl, displacement of the chloro                                  groups by aniline, and reduction.                                              ##STR27##                                                                    1n                                                                            1,5-diamino-2,6-naphthalenedithiol dihydrochloride                            by methods analogous to Monomers 1a and 1i.                                    ##STR28##                                                                    1o                                                                            1,5-diamino-2,6-naphthalenediol dihydrochloride                               prepared from 2,6-dichloro-1,5-dinitro-naphthalene.                            ##STR29##                                                                    1p                                                                            1,2,5,6-tetraminonaphthalene tetrahydrochloride                               prepared by the amination of 2,6-dichloro-1,5-                                dinitro-naphthalene followed by catalytic                                     reduction according to K. Imai, N. Kurihara, L.                               Mathias, J. Wittmann, W. B. Alston, and J. K.                                 Stille, Macromolecules, 6, 158 (1973).                                        ______________________________________                                    

The preferred (1,3) monomers are those wherein Ar¹ is any aromaticmoiety with two sets of ortho-valences at carbon atoms, such as##STR30## wherein β is a bivalent aromatic or heteroaromatic moiety, O,S, SO₂, C═O, --CH₂ CH₂ --, etc.

The four functional groups attached to the valence positions of Ar¹ aredivided into two sets (NH₂ and X₁ H) and (NH₂ and X₂ H) with thefunctional groups within each set being positioned ortho to each otherand the two sets positioned on Ar¹ such that they cannot simultaneouslyreact with the same functional group of another monomer. X₁ and X₂ aredefined as above.

Specific examples of (1,3) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 3below.

                  TABLE 3                                                         ______________________________________                                        Monomers of Type 1, Class 3                                                   ______________________________________                                         ##STR31##                                                                    1q                                                                            3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride                    prepared according to the method of V. V.                                     Korshak, E. S. Krongauz, A. P. Travnikova, A. L.                              Rasanov, and A. D. Katsarava, Dokl, Akad. Nauk.                               SSSR, 196, 106 (1971).                                                         ##STR32##                                                                    1r                                                                            3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride                         obtained commercially from Pfaltz & Bauer.                                     ##STR33##                                                                    1s                                                                            3,3'-dihydroxy-4,4'-diaminodiphenyl ether                                     is prepared according to the method of S. U.                                  Kantor and J. Sonnenberg, U.S. Pat. No. 3,306,876                             (1967).                                                                        ##STR34##                                                                    1t                                                                            3,3'-diamino-4,4'-dihydroxydiphenyl ether                                     prepared according to the method of A. S.                                     Lindsey, S. E. Hunt, and G. K. L. Gibson, U.K.                                Patent No. 1,181,531 (1970).                                                   ##STR35##                                                                    1u                                                                            3,3',4,4'-tetraaminodiphenyl sulfone                                          prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by acetylation,                                       dinitration, hydrolysis, and reduction.                                        ##STR36##                                                                    1v                                                                            3,3'-dimercapto-4,4'-diaminodiphenyl sulfone                                  prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by methods analogous to                               the preparation of 1a and 1i.                                                  ##STR37##                                                                    1w                                                                            3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone                                   prepared according to the method of G. I. Braz,                               I. Y. Kardash, and V. S. Yakubovich, Polym. Sci.                              USSR., 8, page 2013 (1967).                                                    ##STR38##                                                                    1x                                                                            3,3'-diamino-4,4'-dihydroxydiphenyl sulfone                                   prepared from commercially available 4,4'-                                    dihydroxydiphenyl sulfone by acetylation,                                     dinitration, hydrolysis and reduction.                                         ##STR39##                                                                    1y                                                                            3,3',4,4'-tetraaminobenzophenone                                              available commercially from Polysciences, Inc.                                 ##STR40##                                                                    1z                                                                            3,6-diamino-1,2-benzenedithiol dihydrochloride                                prepared by isolation of 2,7-diaminobenzo[1,2-                                d;6,5-d']bisthiazole from the scheme to prepare                               1a followed by hydrolysis.                                                    ______________________________________                                    

Type 2 monomers has the general formula

    Z.sub.1 --Y.sup.2 --Z.sub.2                                2

wherein Y² is a bivalent organic group and Z₁ and Z₂ areelectron-deficient carbon groups and may be the same or different groupsselected from the following class:

    ______________________________________                                        --COOH     --CSSH     --COBr     --CSI                                        --CSOH     --COCl     --CSBr     --CONHR.sub.1                                --COSH     --CSCl     --COI      --CSNHR.sub.1                                                                 --CN                                         ______________________________________                                    

(R₁ =H or an organic group bonded to N by a carbon atom)

The only requirement of Z₁ and Z₂ is that they react with the X₁ H andX₂ H and with the two hydrogen atoms of the primary amino groups of Type1 monomers to form suitable leaving entities, such as water, hydrogensulfide, hydrogen halide, ammonia, etc.

The bivalent group Y² may be an aromatic group, an acyclic aliphaticgroup, or a cycloaliphatic group, and such groups may be substituted byhydrocarbon groups (aliphatic or aromatic) and by hetero atoms andgroups. In general any of groups described above as substituents of thearomatic ring or rings of Ar¹ may be used subject to the samerestrictions.

Formula 2 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (2,1), Class 2 (2,2),and Class 3 (2,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (2,1) monomers are those wherein Y² is nil, or Y₂ compriseat least two carbon atoms to which are attached Z₁ and Z₂ such that thetwo exocyclic bonds between Y² and Z₁ and between Y² and Z₂ have a rigidand fixed relationship to each other and are substantially collinear, orY² may also be a cycloaliphatic group that has at least two carbon atomsto which are attached Z₁ and Z₂ such that the two bonds between Y² andZ₁ and between Y² and Z₂ have a highly preferred relationship to eachother that is substantially collinear. Carboxylic acid derivatives of2j-2q and 2z (as herein described below) such as COOH that decarboxylateat temperatures below that required for polycondensation with Type 1monomers are less preferred.

Specific examples of (2,1) monomers preferred for use in the inventioninclude those monomers in Table 4 below.

                  TABLE 4                                                         ______________________________________                                        Monomers of Type 2, Class 1                                                   ______________________________________                                         ##STR41##                                                                    2a                                                                            terephthalic acid                                                             obtained from Amoco Chemicals Co. and micronized                              and dried before use.                                                          ##STR42##                                                                    2b                                                                            terephthaloyl chloride                                                        obtained from Aldrich and sublimed immediately                                before use.                                                                    ##STR43##                                                                    2c                                                                            1,4-benzenedicarboxamide                                                      prepared from 2b or obtained commercially from                                Pfaltz and Bauer.                                                              ##STR44##                                                                    2d                                                                            terephthalonitrile                                                            obtained from Pfaltz and Bauer.                                                ##STR45##                                                                    2e                                                                            trans-1,4-cyclohexanedicarboxylic acid                                        obtained from Aldrich and recrystallized from                                 water.                                                                         ##STR46##                                                                    2f                                                                            trans-1,4-cyclohexanedicarboxylic acid chloride                               prepared from 2e.                                                              ##STR47##                                                                    2g                                                                            trans-1,4-cyclohexanedicarboxamide                                            prepared from 2f.                                                              ##STR48##                                                                    2h                                                                            trans-1,4-dicyanocyclohexane                                                  prepared from 2g.                                                              ##STR49##                                                                    2i                                                                            2,5-pyridinedicarboxylic acid                                                 obtained from Aldrich Chemical Co.                                             ##STR50##                                                                    2j                                                                            2,6-benzo[1,2-d:4,5-d']bisthiazoledinitrile                                   prepared by diazotization of 2,6-                                             diaminobenzobisthiazole (see reference for 1a)                                followed by treatment with cuprous cyanide.                                    ##STR51##                                                                    2k                                                                            2,6-benzo[1,2,-d:5,4-d']bisoxazoledinitrile                                   prepared from the condensation of compound 1b                                 with urea followed by diazotization as for                                    compound 2j.                                                                   ##STR52##                                                                    2l                                                                            2,6-benzobisimidazoledinitrile                                                prepared as for 2k using compound 1c.                                          ##STR53##                                                                    2m                                                                            2,6-benzo[1,2-d:4,5-d']bisoxazoledinitrile                                    prepared as described for 2k using compound 1d.                                ##STR54##                                                                    2n                                                                            2,6-pyridobisimidazoledinitrile                                               prepared as for 2k using compound 1e.                                          ##STR55##                                                                    2o                                                                            2,6-pyrido[2,3-d:6,5-d']bisoxazoledinitrile                                   prepared as for 2k using compound if.                                          ##STR56##                                                                    2p                                                                            2,6-pyrido[2,3-d:5,6-d']bisthiazoledinitrile                                  prepared as for 2j, using 2,6-                                                diaminopyridobisthiazole as prepared                                          in the synthesis of 1g.                                                        ##STR57##                                                                    2q                                                                            1,7-diphenyl-2,6-benzobisimidazoledinitrile                                   prepared as for 2k using compound 1h.                                          ##STR58##                                                                    2r                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisthiazole                        prepared by the condensation of compound 1a with                              p-toluic acid followed by oxidation.                                           ##STR59##                                                                    2s                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:5,4-d']bisoxazole                         prepared by the condensation of 1b with p-toluic                              acid followed by oxidation.                                                    ##STR60##                                                                    2t                                                                            2,6-bis(4-carboxyphenyl)benzobisimidazole                                     prepared by a method similar to 2s using 1c.                                   ##STR61##                                                                    2u                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisoxazole                         prepared by method similar to 2s using 1d.                                     ##STR62##                                                                    2v                                                                            2,6-bis(4-carboxyphenyl)pyridobisimidazole                                    prepared by a method similar to 2s using 1e.                                   ##STR63##                                                                    2w                                                                            2,6-bis(4-carboxyphenyl)pyrido[2,3-d:6,5-d']bisoxazole                        prepared by a method similar to 2s using 1f.                                   ##STR64##                                                                    2x                                                                            2,6-bis(4-carboxyphenyl)pyrido[2,3-d:5,6-d']bisthiazole                       prepared by a method similar to 2s using 1g.                                   ##STR65##                                                                    2y                                                                            1,7-diphenyl-2,6-bis(4-carboxyphenyl)benzobisimidazole                        prepared by a method similar to 2s using 1h.                                   ##STR66##                                                                    2z                                                                            oxamide                                                                       obtained from Aldrich Chemical Co.                                            ______________________________________                                    

The preferred (2,2) monomers are those wherein Y² comprise twosix-membered rings attached by a covalent carbon-carbon bond each withvalences on the 4-position or each with valences on the 3-position, suchas 4,4'-biphenyl or 3,3'-biphenyl, or Y² comprise two fused six-memberedrings with valence positions being on carbon atoms and having a 1,5relationship to each other, such as 2,6-naphthalene or 2,6-quinoline, orY² is a cycloaliphatic divalent moiety with valences on carbon atoms andin a 1,2-trans configuration, or Y² is a variety of condensed aromaticand heteroaromatic ring systems attached only by carbon-carbon bonds andhaving 2 valences, Z₁ and Z₂ are the same as defined above.

Specific examples of (2,2) monomers preferred for use in the inventioninclude those monomers in Table 5 below.

                  TABLE 5                                                         ______________________________________                                        Monomers of Type 2, Class 2                                                   ______________________________________                                         ##STR67##                                                                    4,4'-biphenyldicarboxylic acid                                                obtained from Aldrich Chemical Co.                                             ##STR68##                                                                    4,4'-biphenyldicarboxylic acid chloride                                       prepared from 2aa.                                                             ##STR69##                                                                    2,6-naphthalenedicarboxylic acid                                              prepared according to the method of B. Raecke and                             H. Schirp. Org. Syn. Coll. Vol. V. page 813                                   (1973) from commercially available 1,8-                                       naphthalenedicarboxylic anhydride.                                             ##STR70##                                                                    2,6-naphthalenedicarboxylic acid chloride                                     prepared from 2cc by treatment with thionyl chloride.                          ##STR71##                                                                    2,6-quinolinedicarboxylic acid                                                prepared from commercially available (Aldrich)                                2,6-dimethyl quinoline by oxidation.                                           ##STR72##                                                                    3,3' -biphenyldicarboxylic acid                                               prepared from o-nitrobenzoic acid by the method                               of M. Kurihara and N. Yoda. J. Macromol. Sci.                                 Chem A1(6), page 1069 (1967).                                                  ##STR73##                                                                    trans-1,2-cyclohexanedicarboxylic acid                                        was obtained from Aldrich Chemical Co. and                                    recrystallized from methanol before use.                                       ##STR74##                                                                    1,4-bis(5-carboxybenzoxazole-2-yl)benzene                                     prepared by the method of J. Preston, W. De                                   Winter and W. L. Hofferbert, J. Heterocyclic                                  Chem. 5, page 269 (1968).                                                      ##STR75##                                                                    1,4-bis(6-carboxybenzothiazole)-2-yl)benzene                                  prepared by methods analogous to 2hh.                                          ##STR76##                                                                    2,5-bis(6-carboxybenzothiazole-2-yl)pyridine.                                 prepared by methods analogous to 2hh.                                         ______________________________________                                    

The preferred (2,3) monomers are those wherein Y² may be any anionic,heteroaromatic and aliphatic divalent species not previously described.

Specific examples of (2,3) monomers preferred for use in the inventioninclude those monomers in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Monomers of Type 2, Class 3                                                   ______________________________________                                         ##STR77##                                                                    4,4'(p-phenylenedioxy)dibenzoyl chloride                                      prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR78##                                                                    4,4'(p-phenylenedioxy)dibenzonitrile                                          prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20(1), page 179 (1979).                                            ##STR79##                                                                    4,4'-(m-phenylenedioxy)dibenzoic acid                                         prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20(1), page 179 (1979).                                            ##STR80##                                                                    4,4'-(m-phenylenedioxy)dibenzoyl chloride                                     from 2mm according to method of R. C. Evers, F.                               E. Arnold, and T. E. Helminiak, Macromolecules,                               14, page 925 (1981).                                                           ##STR81##                                                                    4,4'-(m-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR82##                                                                    3,3'-(m-phenylenedioxy)dibenzoyl chloride                                     according to the method of R. C. Evers, F. E.                                 Arnold, and T. E. Helminiak Maromolecules, 14,                                page 925 (1981).                                                               ##STR83##                                                                    3,3'-(p-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR84##                                                                    4,4'-(o-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR85##                                                                    isophthalic acid obtained from                                                Pfaltz and Bauer and recrystallized                                           from 90% ethanol.                                                              ##STR86##                                                                    4,4'-dicarboxydiphenyl ether                                                  obtained from Polysciences, Inc.                                               ##STR87##                                                                    3,3'-dicarboxydiphenyl ether                                                  prepared from a coupling of m-cresol and m-                                   bromotoluene followed by oxidation by the method                              of M. Tomita, J. Pharm. Soc., Japan, 57, page                                 391 (1937).                                                                    ##STR88##                                                                    succinic acid obtained                                                        from Aldrich Chemical Co.                                                      ##STR89##                                                                    glutaric acid obtained                                                        from Aldrich Chemical Co.                                                      ##STR90##                                                                    adipic acid obtained                                                          from Aldrich Chemical Co.                                                      ##STR91##                                                                    pimelic acid obtained from                                                    Aldrich Chemical Co.                                                           ##STR92##                                                                    sebacic acid obtained from                                                    Aldrich Chemical Co.                                                          ______________________________________                                    

Type 3 monomers has the general formula ##STR93## wherein Ar³ is atrivalent aromatic or heteroaromatic moiety, and X₃ is O, S, or N-R (R═Hor an organic group).

Formula 3 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into two groups: Class 1 (3,1) and Class 2 (3,2).The first number of the number pairs denotes the monomer type and thesecond number of the pairs denotes the monomer class.

The preferred (3,1) monomers are those wherein Z₃ is the same as definedfor Z₁, Ar³ is a trivalent aromatic or heteroaromatic moiety with thethree valence positions being on carbon atoms and having therelationship that the valence bond between Z₃ and Ar³ is nearlycollinear with the same valence bond in subsequently condensed monomers,and X₃ is defined as for X₁ in Table 1. X₃ and NH₂ are positioned orthoto each other on Ar³.

Specific examples of (3,1) monomers preferred for use in the inventioninclude the monomer in Table 7 below.

                  TABLE 7                                                         ______________________________________                                        Monomers of Type 3, Class 1                                                   ______________________________________                                         ##STR94##                                                                    2-(4-carboxyphenyl)-5,6-diaminobenzimidazole                                  dihydrochloride                                                               prepared according to R. F. Kovar, and F. E.                                  Arnold, J. Polym. Sci. Polym. Chem. Ed., 14, page                             2807 (1976).                                                                  ______________________________________                                    

The preferred (3,2) monomers are those wherein Z₃, Ar³, and X₃ aredefined as above. The bonds that are formed in homopolymerization of(3,2) monomers are defined in their spatial relationship having an angleof catenation of about 150° to about 180°.

Specific examples of (3,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 8below.

                  TABLE 8                                                         ______________________________________                                        Monomers of Type 3, Class 2                                                   ______________________________________                                         ##STR95##                                                                    3-mercapto-4-aminobenzoic acid hydrochloride                                  prepared according to Wolfe, AFOSR Final Technical                            Report, Dec. 15, 1980.                                                         ##STR96##                                                                    3-mercapto-4-aminobenzoic acid                                                prepared as described in Example 5.                                            ##STR97##                                                                    3-hydroxy-4-aminobenzoic acid hydrochloride                                   prepared as described by Y. Imai, K. Uno, and Y.                              Iwakura, Makromol. Chem., 83, 179 (1965).                                      ##STR98##                                                                    3-amino-4-hydroxybenzoic acid hydrochloride                                   prepared as described by K. Auwers and H. Rohrig.                             Chem. Ber., 30, 992 (1897).                                                    ##STR99##                                                                    3,4-diaminobenzoic acid                                                       obtained from Aldrich Chemical Co. and                                        recrystallized from deoxygenated water before                                 use.                                                                           ##STR100##                                                                   N.sup.3phenyl-3,4-diaminobenzoic acid                                         prepared from p-aminobenzoic acid by                                          chlorination, oxidation to 3-chloro-4-                                        nitrobenzoic acid, followed by anilation and                                  reduction.                                                                     ##STR101##                                                                   N.sup.4phenyl-3,4-diaminobenzoic acid                                         prepared by nitration of commercially available                               (Aldrich) p-chlorobenzoic acid, followed by                                   anilation and reduction.                                                       ##STR102##                                                                   4-carboxy-3'-mercapto-4'-aminobiphenyl                                        prepared by nitration of commercially available                               4-carboxybiphenyl (ICN/K and K) and reduction to                              4-amino-4'-carboxybiphenyl, followed by placement                             of the o-mercapto group by methods analogous to                               those described for 3a.                                                        ##STR103##                                                                   4-carboxy-3'-amino-4'-hydroxybiphenyl                                         prepared by the nitration of commercially                                     available (ICN/K and K) 4-carboxybiphenyl,                                    conversion to 4-carboxy-p-phenol by reduction and                             diazotization, followed by acetylation,                                       nitration, hydrolysis, and reduction.                                          ##STR104##                                                                   4-carboxy-3',4'-diaminobiphenyl                                               prepared by acetylation of 4-amino-4'-                                        carboxylbiphenyl (see preparation of 3h) followed                             by nitration, hydrolysis, and reduction.                                      ______________________________________                                    

Type 4 monomers have the general formula ##STR105## wherein Z₄, Z₅, Z₆,and Z₇ are the same or different and are chosen from the list ofcarboxylic acid derivatives given for Z₁ in Table 4. Z₄ and Z₅, or Z₆and Z₇, or both sets can also be carboxylic acid anhydride groups. Ar⁴is an aromatic or aromatic heterocyclic moiety having four valencepositions at carbon atoms. Ar⁴ can be a six-member ring with the valencepositions having 1, 2, 4, 5 relationship, or Ar⁴ can be two condensedsix-member rings, such as naphthalene. Z₄ and Z₅ as one set and Z₆ andZ₇ as another set must either be ortho-positioned within each set orbear a 1, 4, 5, 8 relationship to each other. An (imaginary) lineperpendicular to the bond between the valence carbons attached to Z₄ andZ₅ must be collinear with the corresponding (imaginary) line for Z₆ andZ₇.

Formula 4 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (4,1). The first number of the number pairsdenotes the monomer type and the second number of the pairs denotes themonomer class.

Specific examples of (4,1) monomers preferred for use in the inventioninclude those monomers in Table 9 below.

                  TABLE 9                                                         ______________________________________                                        Monomers of Type 4, Class 1                                                   ______________________________________                                         ##STR106##                                                                   4a                                                                            pyromellitic dianhydride                                                      obtained from Aldrich Chemical Co. and sublimed                               or recrystallized (acetic anhydride) before use.                               ##STR107##                                                                   4b                                                                            1,4,5,8-naphthalenetetracarboxylic dianhydride                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 5 monomers has the general formula ##STR108## wherein Z₈ and Z₉ aredefined as for Z₄ and Z₅ in Table 9. Ar⁵ is defined as in Table 9, thetwo amino groups are ortho to each other, and Z₈, Z₉, and the two aminogroups are positioned such that two imaginary lines drawn perpendicularto the bonds between their valence carbons are collinear.

Formula 5 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (5,1). The number pair (5,1) has the samesignificance as above.

Specific examples of (5,1) monomers preferred for use in the inventioninclude the monomer in Table 10 below.

                  TABLE 10                                                        ______________________________________                                        Monomers of Type 5, Class 1                                                   ______________________________________                                         ##STR109##                                                                   5a                                                                            4,5-diaminonaphthalene-1,8-dicarboxylic anhydride                             prepared from the dinitroderivative by chemical                               reduction according to I. Honda and M. Okazaki,                               J. Soc. Org. Synthetic Chem. (Japan), 7, page 25(1950).                       ______________________________________                                    

Type 6 monomer has the general formula ##STR110## wherein Ar⁶ representsan aromatic moiety and is a tetrahydroxy fused ring system, Z₁₀, Z₁₁,Z₁₂, Z₁₆ are the same HO atoms bonded to carbon atoms of Ar⁶.

In general, Ar⁶ may comprise a single or a plurality of aromatic ringsin the center of a completely conjugated fused ring system. The centeraromatic ring or rings of the completely conjugated fused ring systemcan be any of those described above, and others.

Formula 6 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsobe further classified into two groups: Class 1 (6,1), and Class 2 (6,2).The number pairs have the same significance as above.

The preferred (6,1) monomers are those wherein Ar⁶ comprise a singlecenter aromatic ring in the center of the fused ring system.

The preferred (6,2) monomers are those wherein Ar⁶ comprise at least twocenter aromatic rings in the center of the fused ring system.

Specific examples of (6,1) and (6,2) preferred for use in the inventioninclude those monomers in Tables 11 and 12 respectively.

                  TABLE 11                                                        ______________________________________                                        Monomers of Type 6, Class 1                                                   ______________________________________                                         ##STR111##                                                                   6a                                                                            2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene                               prepared from condensation of 1,2,4,5-                                        tetraaminobenzene with oxalic acid according to                               H. Tadamus, F. DeSchryver, W. DeWinter, and C.                                S. Marvel, J. Polym. Sci. A-1,4, page 2831(1966).                             ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Monomers of Type 6, Class 2                                                   ______________________________________                                         ##STR112##                                                                   6b                                                                            2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline                                     prepared from condensation of 3,3'-diaminobenzidine                           with oxalic acid according to method of                                       H. Tadamus, et al., J. Polym. Sci. A-1,4, page 2831(1966).                    ______________________________________                                    

Type 7 monomer has the general formula ##STR113## wherein Y⁷ representsan aromatic or heteroaromatic moiety and is a fused ring carbon group,and X₇ 's are double bonded to carbon of Y⁷.

Formula 7 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (7,1). The number pair (7,1) has the samesignificance as above.

A specific example of (7,1) preferred for use in the present inventionis 7a in Table 13 below.

                  TABLE 13                                                        ______________________________________                                        Monomers of Type 7, Class 1                                                   ______________________________________                                         ##STR114##                                                                   7a                                                                            1,2,6,7-tetraketopyrene                                                       M. Corell, and H. Streck, Ann. 531, page 6(1937).                             ______________________________________                                    

Type 8 monomer has the general formula ##STR115## wherein Y⁸ is a singlecarbon cyclic moiety, X₁₀ and X₁₁ are HO and O atoms respectively,bonded to carbon atoms of Y⁸.

Formula 8 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (8,1). The number pair (8,1) has the samesignificance as above.

A specific example of (8,1) preferred for use in the present inventionis 8a in Table 14 below.

                  TABLE 14                                                        ______________________________________                                        Monomers of Type 8, Class 1                                                   ______________________________________                                         ##STR116##                                                                   8a                                                                            2,5-dihydroxy-1,4-benzoquinone                                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 9 monomers has the general formula ##STR117## wherein Ar⁹represents an aromatic moiety and is a partially fused ring system, Z₁₄and Z₁₅ are OH atoms, X₄ are selected from the class O, S, and NR; R isH or an organic group attached to N; NH₂, X₄ H, Z₁₄, and Z₁₅ are bondedto carbon atoms of Ar⁹ ; NH₂ and X₄ H are positioned ortho; Z₁₄ and Z₁₅are positioned ortho.

Formula 9 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the pesent invention can beclassified as Class 1 (9,1). The number pair (9,1) has the samesignificance as above.

A specific example of (9,1) preferred for use in the present inventionis 9a in Table 15 below.

                  TABLE 15                                                        ______________________________________                                        Monomers of Type 9, Class 1                                                   ______________________________________                                         ##STR118##                                                                   9a                                                                            2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride                          prepared from 1,2-diamino-4,5-dinitrobenzene by                               condensation with oxalic acid followed by reduction                           according to R. F. Kovar and F. E. Arnold,                                    J. Polym. Sci., Polym. Chem. Ed., 14, page 2807(1976).                        ______________________________________                                    

All of the above-cited patents and/or publications of Tables 1-15 arespecifically incorporated herein by reference.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas I-VIII homopolymers may be illustrated bythe following general reaction system: ##STR119##

Representative examples of suitable homopolymers forming liquidcrystalline homopolymer compositions in accordance with the practice ofthe present invention (provided they fall within the above-definedgeneral formulas I-VIII) include the following polymers. For the sake ofconvenience, polymer formulas are hereinbelow shown in simplifiedrepresentation. As an example, --AI]_(n) is ##STR120## The structuresrepresenting --AI] are defined in the Appendix --A] has the structure##STR121## and --I] has the structure ##STR122##

Their sequential combination is therefore ##STR123## All simplifiedpolymer formula representations appearing in the specification may bereadily interpreted by reference to the Appendix.

--AI]_(n), --AIBI]_(n), --BI]_(n), and --T]_(n),

--AIDI]_(n), --AIEI]_(n), --AIFI]_(n), --AILI]_(n), --AIMI]_(n),--AINI]_(n),

--ATIT']_(n), --ATKT']_(n), --BIDI]_(n), --BIEI]_(n), --BIFI]_(n),

--BILI]_(n), --BIMI]_(n), --BINI]_(n), --BTIT']_(n), --BTKT']_(n),

--EILI]_(n), --FILI]_(n), --LI]_(n), --TI]_(n), --U]_(n), and --V]_(n),

--A]_(n), --AB]_(n), --AC]_(n), --AE]_(n), --AF]_(n), --AICI]_(n)--AIOI]_(n),

--AIQI]_(n), --AJ]_(n), --AL]_(n), --AM]_(n), --AN]_(n), --AQ]_(n),--AVIV']_(n),

--B]_(n), --BC]_(n), --BD]_(n), --BE]_(n), --BF]_(n), --BICI]_(n),--BIOI]_(n),

--BIQI]_(n), --BJ]_(n), --BL]_(n), --BM]_(n), --BN]_(n), --BQ]_(n),--BVIV']_(n),

--B'A'B'Z]_(n), --B'A'F'Z]_(n), --B'H']_(n) * (* denotes oxygens alwaysmeta on B') --B'I']_(n), --B'P']_(n),

--B'Q']_(n), --B'S']* --C]_(n), --CE]_(n), --CF]_(n), --CI]_(n),--CIEI]_(n),

--CIFI]_(n), --CILI]_(n), --CIMI]_(n), --CINI]_(n), --CIOI]_(n),--CJ]_(n),

--CL]_(n) --CM]_(n), --CN]_(n), --CTIT']_(n), --CTKT']_(n),--C'A'B'Z]_(n),

--C'A'F'Z]_(n), --D'A'B'Z]_(n), --D'A'F'Z]_(n), --E]_(n), --EF]_(n),

--EI]_(n), --EIFI]_(n), --EIMI]_(n), --EINI]_(n), --EIOI]_(n),--EIQI]_(n),

--EJ]_(n), --EL]_(n), --EM]_(n), --EN]_(n), --ETIT']_(n), --ETKT']_(n),

--E'A'B'Z]_(n), --E'A'F'Z]_(n), --F]_(n), --FI]_(n), --FIMI]_(n),

--FINI]_(n), --FIOI]_(n), --FJ]_(n), --FL]_(n), --FM]_(n), --FN]_(n),--F'A']_(n),

--L]_(n), --LJ]_(n), --LTIT']_(n), --LTKT']_(n), --M]_(n), --MI]_(n),--MTIT']_(n),

--MTKT']_(n), --N]_(n), --NI]_(n), --NTIT']_(n), --NTKT']_(n),--QI]_(n),

--QJ]_(n), --RI]_(n), --RJ]_(n), and --UI]_(n),

--AD]_(n), --AG]_(n), --AH]_(n), --AIGI]_(n), --AIHI]_(n), --AIPI]_(n),

--AIRI]_(n), --AISI]_(n), --AK]_(n), --AO]_(n), --AP]_(n), --AR]_(n),--AS]_(n), --BG]_(n),

--BIGI]_(n), --BH]_(n), --BIHI]_(n), --BIPI]_(n), --BIRI]_(n),--BISI]_(n),

--BK]_(n), --BO]_(n), --BP]_(n), --BR]_(n), --BS]_(n), --B'G']_(n),

--B'H']_(n) ** (** denotes oxygen always para on B'),

--B'J']_(n), --B'K']_(n) * (* denotes oxygens always meta on B'),

--B'K']_(n) **, --B'L']_(n), --B'M']_(n), --B'N']_(n), --B'O']_(n),

--B'R']_(n), --B'S']_(n) **, --B'U']_(n), --CD]_(n), --CG]_(n),--CH]_(n),

--CIDI]_(n), --CIGI]_(n), --CIHI]_(n), --CIPI]_(n), --CIQI]_(n),--CIRI]_(n),

--CISI]_(n), --CK]_(n), --CO]_(n), --CP]_(n), --CQ]_(n), --CR]_(n),--CS]_(n),

--CVIV']_(n), --C'G']_(n), --C'H']_(n), --C'I']_(n), --C'J']_(n),--C'K']_(n),

--C'L']_(n), --C'O']_(n), --C'Q']_(n), --C'R']_(n), --C'S']_(n),

--D]_(n), --DE]_(n), --DF]_(n), --DG]_(n), --DH]_(n), --DI]_(n),--DIEI]_(n),

--DIFI]_(n), --DIGI]_(n), --DIHI]_(n), --DILI]_(n), --DIMI]_(n),--DINI]_(n),

--DIOI]_(n), --DIPI]_(n), --DIQI]_(n), --DIRI]_(n), --DISI]_(n),

--DJ]_(n), --DK]_(n), --DL]_(n), --DM]_(n), --DN]_(n), --DO]_(n),--DP]_(n),

--DQ]_(n), --DR]_(n), --DS]_(n), --DTIT']_(n), --DTKT']_(n),--DVIV']_(n),

--D'G']_(n), --D'H']_(n) * (* denotes oxygen always in 3,3'-positions onD'), --D'H']_(n) ** (** denotes oxygen always in 4,4'-positions on D'),

--D'I']_(n), --D'J']_(n), --D'K']_(n) *, --D'K']_(n) **,

--D'L']_(n), --D'M']_(n), --D'N']_(n), --D'O']_(n), --D'Q']_(n),--D'R']_(n),

--D'S']_(n) *, --D'S']_(n) **, --D'U']_(n), --EG]_(n), --EH]_(n),--EIGI]_(n),

--EIHI]_(n), --EIPI]_(n), --EIRI]_(n), --EISI]_(n), --EK]_(n),--EO]_(n),

--EP]_(n), --EQ]_(n), --ER]_(n), --ES]_(n), --EVIV']_(n), --E'G']_(n),

--E'H']_(n), --E'I']_(n), --E'J']_(n), --E'K']_(n), --E'L']_(n),--E'0']_(n),

--E'Q']_(n), --E'R']_(n), --E'S']_(n), --FG]_(n), --FR]_(n),

--FIGI]_(n), --FIHI]_(n), --FIPI]_(n), --FIQI]_(n), --FIRI]_(n),--FISI]_(n),

--FK]_(n), --FO]_(n), --FP]_(n), --FQ]_(n), --FR]_(n), --FS]_(n),--FTIT']_(n),

--FTKT']_(n), --FVIV']_(n), --G]_(n), --GH]_(n), --GI]_(n), --GIHI]_(n),

--GILI]_(n), --GIMI]_(n), --GINI]_(n), --GIOI]_(n), --GIPI]_(n),--GIQI]_(n),

GIRI]_(n), --GISI]_(n), --GJ]_(n), --GK]_(n), --GL]_(n), --GM]_(n),--GN]_(n),

--GO]_(n), --GP]_(n), --GQ]_(n), --GR]_(n), --GS]_(n), --GTIT']_(n),

--GTKT']_(n), --GVIV']_(n), --H]_(n), --HI]_(n), --HILI]_(n),

--HIMI]_(n), --HINI]_(n), --HIOI]_(n), --HIPI]_(n), --HIQI]_(n),--HIRI]_(n),

--HISI]_(n), --HJ]_(n), --HK]_(n), --HL]_(n), --HM]_(n), --HN]_(n),--HO]_(n),

--HP]_(n), --HQ]_(n), --HR]_(n), --HS]_(n), --HTIT']_(n),

--HTKT']_(n), --HVIV']_(n), --LK]_(n), --LVIV']_(n),

--MJ]_(n), --MK]_(n), --MVIV']_(n), --NJ]_(n), --NK]_(n),

--NVIV']_(n), --OI]_(n), --OJ]_(n), --OK]_(n), --OTIT']_(n),

--OTKT']_(n), --OVIV']_(n), --PI]_(n), --PJ]_(n), --PK]_(n),

--PTIT']_(n), --PTKT']_(n), --PVIV']_(n), --Q]_(n), --QK]_(n),

--QTIT']_(n), --QTKT']_(n), --QVIV']_(n), --R]_(n), --RK]_(n),

--RTIT']_(n), --RTKT']_(n), --RVIV']_(n), --SI]_(n), --SJ]_(n),

--SK]_(n), --STIT']_(n), --STKT']_(n), --SVIV']_(n), --W]_(n),

--X]_(n), and --Y]_(n).

The most preferred extended chain homopolymers in accordance with thepractice of the present invention include

--AI]_(n), --AIBI]_(n), --BI]_(n), and --T]_(n).

The especially preferred extended chain homopolymers in accordance withthe practice of the present invention include

--AIDI]_(n), --AIEI]_(n), --AIFI]_(n), --AILI]_(n), --AIMI]_(n),--AINI]_(n),

--ATIT']_(n), --ATKT']_(n), --BIDI]_(n), --BIEI]_(n), --BIFI]_(n),

--BILI]_(n), --BIMI]_(n), --BINI]_(n), --BTIT']_(n), --BTKT']_(n),

--EILI]_(n), --FILI]_(n), --LI]_(n), --TI]_(n), --U]_(n), and --V]_(n).

The preferred extended chain homopolymers in accordance with thepractice of the present invention include

--A]_(n), --AB]_(n), --AC]_(n), --AE]_(n), --AF]_(n), --AICI]_(n),--AIOI]_(n),

--AIQI]_(n), --AJ]_(n), --AL]_(n), --AM]_(n), --AN]_(n), --AQ]_(n),--AVIV']_(n),

--B]_(n), --BC]_(n), --BD]_(n), --BE]_(n), --BF]_(n), --BICI]_(n),--BIOI]_(n),

--BIQI]_(n), --BJ]_(n), --BL]_(n), --BM]_(n), --BN]_(n), --BQ]_(n),--BVIV']_(n),

--B'A'B'Z]_(n), --B'A'F'Z]_(n), --B'H']_(n) * (* denotes oxygens alwaysmeta on B') --B'I']_(n), --B'P']_(n),

--B'Q']_(n), --B'S']*--C]_(n), --CE]_(n), --CF]_(n), --CI]_(n),--CIEI]_(n),

--CIFI]_(n), --CILI]_(n), --CIMI]_(n), --CINI]_(n), --CIOI]_(n),--CJ]_(n),

--CL]_(n), --CM]_(n), --CN]_(n), --CTIT']_(n), --CTKT']_(n),--C'A'B'Z]_(n),

--C'A'F'Z]_(n), --D'A'B'Z]_(n), --D'A'F'Z]_(n), --E]_(n), --EF]_(n),

--EI]_(n), --EIFI]_(n), --EIMI]_(n), --EINI]_(n), --EIOI]_(n),--EIQI]_(n),

--EJ]_(n), --EL]_(n), --EM]_(n), --EN]_(n), --ETIT']_(n), --ETKT']_(n),

--E'A'B'Z]_(n), --E'A'F'Z]_(n), --F]_(n), --FI]_(n), --FIMI]_(n),

--FINI]_(n), --FIOI]_(n), --FJ]_(n), --FL]_(n), --FM]_(n), --FN]_(n),--F'A']_(n),

--L]_(n), --LJ]_(n), --LTIT']_(n), --LTKT']_(n), --M]_(n), --MI]_(n),--MTIT']_(n),

--MTKT']_(n), --N]_(n), --NI]_(n), --NTIT']_(n), --NTKT']_(n),--QI]_(n),

--QJ]_(n), --RI]_(n), --RJ]_(n), and --UI]_(n).

It is helpful to define three P₂ O₅ contents, operative at differentstages of polymerization, that must be controlled in order to optimizethe synthesis procedure of the present invention. We will define theinitial P₂ O₅ content m_(o) as the P₂ O₅ content of the polyphosphoricacid operative during dehydrohalgenation (in step b above and asexplained more fully hereinafter). The initial P₂ O₅ content inaccordance with the practice of the instant invention should be belowabout 83.3%, and may range from between about 83.3% to about 63%;preferrably below about 82%, more preferrably below about 80%, and mostpreferrably below about 76%.

The intermediate P₂ O₅ content is operative at the initiation ofpolycondensation and is calculated so as to give the third (or final) P₂O₅ content f that accounts for polyphosphoric acid hydrolysis by 100% ofthe theoretical water of polycondensation. The final P₂ O₅ content, f,must be above some minimum value if the solution is to maintain itseffectiveness as a reaction medium at the late stages of polymerization.The final P₂ O₅ content should be between about 82% to about 86%,preferrably between about 82% to about 84%, and most preferrably betweenabout 82% to about 83%.

The various important general process steps for preparing liquidcrystalline polymer compositions of the present invention may includeone or more of the following stages which are considered to be withinthe process parameters described above. These stages are:

Stage One--One or more of a selected first monomers selected from thegroup consisting of (amino-group-containing) monomers 1, 3, 5, or 9 isadded to a specified initial weight in grams (given by a*) of apolyphosphoric acid with a P₂ O₅ content m_(o) according to theempirical equation

    a* ={[1-f]([P.sub.y /P.sub.c ]-P.sub.y)-[n.sub.o (18.02)/M.sub.w ]P.sub.y }(1-m.sub.o).sup.-1

where P_(y) is the weight in grams of the theoretical yield of polymer,P_(c) is the weight fraction of polymer in the total weight of the finalliquid crystalline polymer composition (and is chosen to be above thecritical concentration of the polymer necessary for liquid crystallinephase formation in the resulting polymer-polyphosphoric acidcomposition), n_(o) is an integer giving the number of moles ofcondensation by-product per mole of polymer repeating unit, the number18.02 is the molecular weight of the condensation by-product, M_(w) ismolecular weight of the polymer repeating unit, and f is the final P₂ O₅content that must be above a minimum value as defined by this invention.

Stage Two--Once the first monomer(s) are combined with polyphosphoricacid, and protecting groups, if present, released, (optionally,depending on the particular polymer and reaction mechanism chosen) astoichiometric amount of one or more of a selected second monomersselected from the group consisting of 2, 4, 6, 7 or 8 is next added andthe chosen value of f is achieved by adding b* (an intermediate weightin grams of P₂ O₅) to the mixture according to the equation.

    b* =[P.sub.y /P.sub.c ]-P.sub.y -[{n.sub.o (18.02)/M.sub.w }]P.sub.y -a*

Stage Three--The resulting mixture (containing the first monomer(s)and/or the second monomer(s)) is then heated to a temperature suitablefor polycondensation. The reaction temperature may range from about 100°C. to about 210° C., preferrably about 110° C. to about 200° C. morepreferrably about 160° C. to about 190° C., and most preferrably about185° C.

The P₂ O₅ content, m_(o), should be low enough to:

(1) achieve efficient dehydrohalogenation and/or

(2) achieve sufficient monomer loading to achieve desired P_(c) withoutfoaming problem or unusually high bulk viscosity. f should be highenough to:

(2a) maintain a polyphosphoric acid composition that is an effectivereaction medium at late stages of polycondensation.

(2b) provide an effective phosphorylating medium as described in N. Yodaand M. Kurihara, "New Polymers of Aromatic Heterocycles byPolyphosphoric Acid Solution Methods", J. Polymer Science,Macromolecular Reviews, Volume 5, (1971), p. 159 at initial stage ofpolymerization. The subject matter of the paper by Yoda and et. al., isspecifically incorporated herein by reference.

(2c) provide an effective solvent for the polymer at the end ofpolycondensation.

Accordingly, it is possible to dehydrohalogenate the selectedhydrohalide (monomers) more rapidly; the foaming problem is alleviatedor eliminated; the solution in PPA of lesser P₂ O₅ content than that ofU.S. Pat. No. 4,225,700 is much less viscous and dehydrohalogenation canbe carried out much more readily. Further, a solution of selectedmonomers in PPA of considerably higher concentration is possible and areaction product containing a much higher concentration of polymer ispossible.

The above-mentioned formulas I, III, V, VII, and VIII homopolymercompositions may be prepared in accordance with the above processparameters by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (1,1), (1,2), or (1,3)with or without oxidation protecting atoms or groups with a preliminarysolvent of phosphoric acid having a relatively low phosphorus pentoxidecontent,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) adding a selected second monomer (for example, a second monomerselected from the group consisting of (2,1), (2,2), (2,3), (4,1), (6,1),(6,2), (7,1) or (8,1)) in the resulting solution of step (b) to providea mixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization.

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect radiation at a rate to form a firsthomooligomeric product having a preselected intrinsic viscosity or afirst homopolymeric product.

Formulas II, IV, and VI homopolymer compositions may be prepared by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (3,1), (3,2), (5,1), or(9,1) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent.

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homooligomericproduct having a preselected intrinsic viscosity or a firsthomopolymeric product.

Copolymeric Compositions and their preparation

In accordance with a further aspect of the invention, there is provideda liquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain copolymer having thegeneral formulas: ##STR124## wherein Ar¹ represents an aromatic moietyand is XXX as defined above, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, and Y² is nil or represents a bivalent organic radical and isXXXI as defined above, a_(i) b_(i) represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR125## wherein Ar¹ represents an aromatic moiety and is XXXas defined above, X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ orX₂ of each hetero ring are disposed ortho to one another and Y²represents a bivalent organic radical and is XXXI as defined above,a_(i) b_(i) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, Ar³ represents a different aromatic moietyand is XXII as defined above, the nitrogen atom and X₃ being bonded toaromatic carbon atoms of Ar³, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR126## wherein Ar³ represents an aromatic moietyand is XXII as defined above, X₃ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₃ being bonded toaromatic carbon atoms of Ar³, N and X₃ of each hetero ring are disposedortho to one another, c_(k) represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;##STR127## wherein Ar¹ represents an aromatic moiety and is XXXII asdefined above, Ar⁴ represents a different aromatic moiety and is XXIIIas defined above, the nitrogen atoms being bonded to Ar¹ and the carbonatoms being bonded to Ar⁴, a_(i) b_(j) represents the molar proportionsof the respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR128## wherein Ar⁴ represents a different aromatic moietyand is XXIII as defined above, Ar¹ represents an aromatic moiety and isXXXII as defined above, and Ar⁵ represents an aromatic moiety differentfrom Ar⁴ and Ar¹ and is XXIV as defined above, the carbon atoms beingbonded to Ar⁴ and Ar⁵ and the nitrogen atoms being bonded to Ar¹ andAr⁵, n being a positive integer; c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, a_(i)b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer; ##STR129##wherein Ar¹ represents an aromatic moiety and is XXX as defined above,Ar⁶ represents a different aromatic moiety and is XXV as defined above,X₁ and X₂ are the same or different and are sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the NH groups and X₄ and X₁ beingbonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of eachhereto ring are disposed ortho to one another, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR130## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, Ar⁶ represents adifferent aromatic moiety and is XXV as defined above, X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hereto ring aredisposed ortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar⁹represents an aromatic moiety different from Ar⁶ and Ar¹ and is XXVI asdefined above, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(k) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; or ##STR131## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Y⁷ represents an aromatic or heteroaromaticmoiety and is XXVIII as defined above, the nitrogen atoms being bondedto aromatic carbon atoms of Ar¹ and bonded to adjacent carbon atoms ofY⁷, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XVIII copolymers may be illustrated bythe following general reaction system: ##STR132## The above-mentionedformulas IX, X, XII, XV, XVI, XVII, and XVIII copolymer compositions maybe prepared in accordance with the above process parameters by:

(a) mixing at least two of a selected first monomers (for example, twoor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting solution ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Similarly formulas IX, XII, XVIII, and copolymer compositions may beprepared by:

(a) mixing at least one of a selected first monomers (for example, oneor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) adding at least two of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting solution ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstcooligomeric product having a preselected intrinsic viscosity or a firstcopolymeric product.

Preferred formulas IX, X, XI, XII, XV, XVI, XVII, and XVIII, andcopolymers forming liquid crystalline copolymer compositions of theinstant invention are those wherein a_(i) is the mole fraction of theith monomer selected from Type 1, b_(j) is the mole fraction of the jthmonomer selected from Types 2, 4, 6, 7, or 8, c_(k) is the mole fractionof the kth monomer selected from Types 3, 5, or 9, m and m' areappropriate molar quantities based on desired yiled, a_(i) b_(j) anda_(i) b_(j) m/m+m' are the molar proportions of the recurring unitsresulting from the condensation of the ith monomer of Type 1 and the jthmonomer of Type 2, 4, 6, 7, or 8, c_(k) and c_(k) m'/m+m' are the molarproportions of the recurring unit resulting from the condensation of thekth monomer of Type 3, 5, or 9, y_(ij) is the average block length(i.e., the average number of sequential recurring units unbroken by adifferent recurring unit) of the recurring unit formed from the ithmonomer of Type 1 and the jth monomer of Type 2, 4, 6, 7, or 8, y_(k) isthe average block length of the recurring unit formed byself-condensation of the kth monomer of Type 3, 5, or 9, and n is theaverage overall length of the copolymer (i.e., the average total numberof recurring units independent of structure). The number of recurringunits in the copolymer may be the product of the highest i and thehighest j or may be the product of the highest i and the highest j plusthe highest k. i, j and k can be as high as is practical, but may havecertain minimal values if copolymers, rather than homopolymers, are tobe obtained.

Selected molar quantities (a₁ m, a₂ m, . . . a_(i) m) of monomers ofType 1 may be mixed with a phosphoric acid having a phosphorus pentoxidecontent of from about 63% to about 78%, preferably greater than about68%, most preferably about 78%, and the protecting groups, such ashydrogen halide, if present, may be substantially removed by heating,and applying reduced pressure if desired. The quantity of the phosphoricacid is most desirably determined in accordance with equation a* above,making the necessary calculations for addition of monomers of possiblydifferent molecular weights and different proportions. A stoichiometricquantity (i.e., b₁ m+b₂ m+. . . b_(j) m=m) of monomer selected from Type2, 4, 6, 7, or 8 may then be added to the resulting solution. Thephosphorus pentoxide content of the resulting mixture may then be raisedin accordance with equation b* above, so as to raise the finalphosphorus pentoxide content of the substantially copolymerized mixtureto a value preferably within the range between about 81% to about 84%and most preferably between about 82% to about 83.5%. The resultingmixture may then be heated to a temperature preferably about 100° C. toabout 210° C., most preferably to about 170° C. to about 185° C. withina practical time period, from less than about one hour to greater thanabout 5 hours, preferably within about 1 to about 3 hours. Thetemperature may be maintained for a sufficient time, which may rangefrom less than about 1 hour to about 48 hours or more, most preferablybetween from about 1 to about 23 hours, to achieve the desired n value.The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions comprising copolymers with thegeneral formulas IX, XII, XVI, and XVIII is illustrated for thosecompositions including general formula IX wherein the selected monomersof Type 1 are further classified as being of Types (1,1), (1,2), or(1,3) and the selected monomers of Type 2 are of Types (2,1), (2,2), or(2,3).

General formula IX copolymers prepared from Type (1,1), and Type (2,1)monomers have the advantage that the critical concentration necessaryfor liquid-crystalline behavior is low. For the copolymers listed below,their critical concentration may be as low as about 5 weight percent inpolyphosphoric acid at substantially moderate n values, thus allowing abroad range of operable concentrations. ##STR133## Since the recurringunits of the copolymers are of essentially comparable mesogenicity, abroad range of copolymer compositions may be achieved; for instance, a₁b₁ can range from nearly zero to nearly one while a_(i) b₂ or a₂ b₁(because it is equal to 1-a₁ b₁) ranges from nearly one to nearly zero,respectively. The average block lengths y₁₁ and y₁₂ or y₂₁ are governedby the method of monomer addition described above and the molarquantities selected. Thus, for monomer pairs of essentially equalreactivity, y₁₁, which equals 1/1-a₁ b₁, may range from nearly one tovery high values. In a like manner, y₁₂ or y₂₁ can range from very highvalues to nearly one. Monomer purity, control of stoichiometry, andexclusion of side reactions caused by oxidizing impurities must besufficient to obtain an overall copolymer length, n, greater than about50 in order to obtain the desired polymeric properties of usefulmechanical strength, modulus, etc. The practice of the invention as itrelates to copolymers derived from Class 1 monomers is furtherillustrated in Examples 49-51 and 54-66 below.

General formula IX copolymers may be prepared from type (1,1) (2,1) and(2,2) monomers and from type (1,1), (1,2) and (2,1) monomers. Thesemonomers are classified as Class 2 owing either to a moderately reducedmesogenic character of the recurring unit derived from them or to theirtendency to reduce the solubility range of the resulting polymer, whichin turn is usually owing to an overall reduction of theheteroatom/hydrocarbon ratio of the resulting polymer. Both of theseconditions dictate that incorporation of Class 2 monomers intocopolymers of the present invention should be carefully selected. Thedegree of this selectivity is illustrated by the following copolymersprepared in accordance with the practice of the invention. ##STR134##The immediately preceding list of copolymers is derived from monomercompositions containing monomers imparting reduced solubility to thecopolymer. The preferred values of a₁ b₁ (i.e., the mole fraction of themore soluble recurring unit) are those greater than about 0.8, leadingto values of y₁₁ greater than about 5 and y₁₂ values of nearly one.Monomer purity, control of stoichiometry, exclusion of oxidizingimpurities, and selection of the molar quantity of the less solublemonomer to maintain copolymer solubility must be sufficient to achievean average n value of greater than about 50. Increased proportion of aless soluble monomer may be achieved by selecting comonomers that impartimproved solubility to the copolymer. In general, monomers of Type 1wherein X is S impart greater solubility than those in whic X is O or N.The practice of the invention as it relates to copolymers of partiallyreduced solubility is further illustrated in Examples 52, 53, 70, 71,and 72 below.

The following list of copolymers is derived from incorporation ofmonomers of moderately reduced mesogenicity and the practice of theinvention is illustrated for them. ##STR135## The preferred ranges of a₁b₁ are from nearly zero to nearly one for copolymers in thisclassification with the overall proviso that the overall copolymerconcentration in the polyphosphoric acid be above a criticalconcentration determined by the least mesogenic recurring unit. Thus,above about 13% the above copolymers may have a₁ b₁ values between aboutone and zero, y₁₁ values of nearly one and greater, and y₂₁ values ofnearly one and greater. The preferred concentration with these a₁ b₂ anda₂ b₁ values may be between about 15 and about 22 weight percent. If themolar proportion of the more highly mesogenic recurring unit (i.e., a₁b₁) is selected to have values of greater than about 0.6, preferablygreater than about 0.75, then the range of operable concentrations isincreased to include concentrations of the copolymer in greater thanabout 8 weight percent, preferably above about 10 weight percent. Valuesof n greater than about 50 are preferable as stated above.

General formula IX copolymer compositions may be prepared from Class 3monomers.

Monomers characterized as belonging to Class 3 lead to polymer recurringunits that have little or no mesogenic character. Their incorporationinto copolymers prepared as above are within the scope of the presentinvention but are less preferred because the random incorporation of asignificant molar proportion of these nonmesogenic units leads toinsufficient block length of the mesogenic recurring unit or units toimpart liquid-crystalline behavior. Incorporation of less than about 3molar percent of Class 3 monomers is preferred. Increased incorporationof Class 3 polymers are highly preferred by use of a block polymerprocedure described below. A less preferred embodiment of the presentinvention is the preparation of General formulas X, XV, and XVII by theaddition of monomers of Types 3, 5, and 9, respectively, to the initialsolution of the above copolymer procedure. The unique feature of thegeometry of monomers of Types 3 (except for 3k), 5, and 9 is therequirement that the block lengths, y_(k), be large or, if small, be aneven number. This condition dictates that preferred compositions offormulas X, XV, and XVII are prepared by a block polymer proceduredescribed below.

The general formula XI copolymer composition shown above is preparedaccording to the following procedure:

(a) mixing at leat two of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Selected molar quantities (c₁ m, c₂ m, . . . c_(k) m) of Type 3 monomersmay be mixed with a phosphoric acid having a phosphorus pentoxidecontent of from about 63% to about 78%, preferably greater than about68%, most preferably about 78%, and the protecting groups, if present,may be substantially removed by heating, and applying reduced pressure,if desired. The quantity of phosphoric acid is determined in accordancewith equation a* above, making the necessary calculations for theaddition of monomers of possibly different molecular weights anddifferent proportions. The phosphorus pentoxide content of the resultingmixture may then be raised in accordance with equation b* above, so asto raise the final phosphorus pentoxide of the substantiallycopolymerized mixture to a value greater than about 81%, most preferablybetween about 82% to about 83% but less than about 84%. The resultingmixture may then be heated to about 100° C. to about 200° C., mostpreferably between about 150° C. to about 185° C. within a practicalperiod of time, preferably within a time period of less than about 1hour to about 5 hours or more, and most preferably within a period ofabout 1 hour to about 3 hours, and then maintained at the selectedtemperature for sufficient time to achieve the desired n value.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include copolymers with thegeneral formula XI is further illustrated for those compositions whereinthe selected monomers of Type 3 are further classified as being of Type(3,2).

The polymers ##STR136## are prepared according to the above procedurewherein c₁ is the molar proportion of the more soluble recurring unitand selected to be above about 0.5, more preferably above about 0.7, toensure the solubility of the resulting copolymer to the highconcentrations required for liquid-crystalline behaviour. A weightpercent of the copolymer above about 15 weight percent, more preferablyabove about 17.5 weight percent, may be selected. Molar proportionsselected above and monomer reactivity ratios determine the average blocklengths y₁ and y₂. The block length does not bear on whetherliquid-crystalline behavior in polyphosphoric acid is obtained withthese polymers. The important factor is the maintenance of solubility athigh concentration and the preparation of these copolymers inpolyphosphoric acid at high concentration from monomers.

Blockpolymeric Compositions and their preparation

In accordance with a still further aspect of the invention, there isprovided a liquid-crystalline composition useful in the preparation offibers and films comprising a polycondensation product consistingessentialy of a blend of certain polyphosphoric acids and a highconcentration of at least one high molecular weight extended chain blockpolymer having the general formulas: ##STR137## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR138## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar³ represents an aromatic moiety and is XXII as definedabove, X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₃ being bonded to aromatic carbon atomsof Ar¹, N and X₃ of each hetero ring are disposed ortho to one another,c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR139## wherein Ar³ represents an aromatic moiety and isXXII as defined above, X₃ is sulfur, oxygen, or NR (R being hydrogen oran organic group), the nitrogen atoms and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of each hetero ring are disposed ortho toone another, c_(k) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR140## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Ar⁴ represents a different aromatic moiety andis XXIII as defined above, the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR141## wherein Ar¹ represents an aromaticmoiety and is XXXII or XXX as defined above with the proviso that whenAr¹ is bonded to nitrogen atoms Ar¹ is XXXII and when Ar¹ is bonded toboth nitrogen atoms and X₁ and X₂, Ar¹ is XXX as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the carbon atoms being bonded to Ar⁴, m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y' represents an average number of the respectivedifferent sequential recurring units present in said block polymer, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar⁴, N and X₁ and X₂ of each heteroring are disposed ortho to one another and Y² is nil or represents abivalent organic radical and is XXXI as defined above, m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR142## wherein Ar³ representsan aromatic moiety and is XXII as defined above, X₃ is sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, p represents the molarproportions of the respective different recurring units present in saidblock polymer, y'/2 represents an average number of the respectivedifferent sequential recurring units present in said block polymer, Ar¹represents an aromatic moiety and is XXXII as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, q represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer; ##STR143## wherein Ar⁴represents a different aromatic moiety and is XXIII as defined above,Ar¹ represents an aromatic moiety and is XXXII as defined above, and Ar⁵represents an aromatic moiety different from Ar⁴ and Ar¹ and is XXIV asdefined above, the carbon atoms being bonded to Ar⁴ and Ar⁵ and thenitrogen atoms being bonded to Ar¹ and Ar⁵, n being a positive integer;c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR144## wherein Ar¹represents an aromatic moiety and is XXX as defined above, Ar⁶represents a different aromatic moiety and is XXV as defined above, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR145## wherein Ar¹ represents an aromaticmoiety and is XXX as defined above, Ar⁶ represents a different aromaticmoiety and is XXV as defined above, X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the NH groups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶and Ar¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, Ar⁹ representsan aromatic moiety different from Ar⁶ and Ar¹ and is XXVI as definedabove, X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₄ being bonded to aromatic carbon atoms ofAr⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; or ##STR146## wherein Ar¹ represents an aromaticmoiety and is XXXII as defined above, Y⁷ represents an aromatic orheteroaromatic moiety and is XXVIII as defined above, the nitrogen atomsbeing bonded to aromatic carbon atoms of Ar¹ and bonded to adjacentcarbon atoms of Y⁷, a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XIX block polymers may be illustratedby the following general reaction system: ##STR147## The above-mentionedformulas IX, XII, XVI, XVIII, and XIX block polymer compositions may beprepared in accordance with the above process parameters by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a mixture of the first and secondmonomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), (d),and (e) with the overall proviso that at least one of the selectedmonomer of step (a) or (c) which forms the second homo-oligomericproduct be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, formulas IX, XII, XVI, XVIII, and XIX block polymercompositions may be prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a first mixture of the first and secondmonomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of a different first and secondmonomer in the preliminary solvent, said second mixture being formed bylike steps (a), (b) and (c) with the overall proviso that at least oneof the selected monomer of step (a) or (c) which forms the secondmixture be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (f) to provide a first oligomer-monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(h) causing polymerization of the mixture resulting from step (g) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The above IX-XIX block polymers forming the liquid crystalline blockpolymer compositions of the instant invention can be characterized ashaving more than one recurring unit, the distribution or sequencing ofwhich may be different from that obtained by the random condensation ofmonomers as in the copolymers described above and is furthercharacterized as having contiguous blocks of the same recurring unit asobtained by the random condensation of oligomers.

The preferred formulas IX, XII, XVI, XVIII, and XIX block polymers arethose polymers wherein a_(i) b_(j) is the mole fraction of the recurringunit formed by the condensation of a homo-oligomeric reaction product(defined below) derived from the ith monomer of Type 1 with astoichiometric quantity of jth monomer of Type 2, 4, 6, 7, or 8,respectively, and incorporated by a block-polymeric procedure describedbelow, and y_(ij) and n have the same meaning as described above forcopolymers.

The preferred XI block polymers are those wherein c_(k) is the molefraction of the recurring unit formed by the condensation of ahomo-oligomeric reaction product (defined below) derived from the kthmonomer of Type 3 and incorporated by a block polymeric proceduredescribed below, and y_(k) and n are as defined for copolymers.

The preferred X, XV, and XVII block polymers are those wherein a_(i)b_(j) m/m+m' is the mole fraction of the recurring unit formed by thecondensation of m moles of recurring units of a homo-oligomeric reactionproduct derived from the ith monomer of Type 1 and the jth monomer ofType 2, 4, or 6 and combined with m' moles of recurring units of ahomo-oligomeric reaction product derived from condensation of the kthmonomer of Type 3, 5, or 9, respectively, and y_(ij), y_(k), and n areas defined for copolymers.

The preferred XIII block polymers are those wherein m' and m areappropriate molar quantities of the monomers that form the reactionproducts and are selected to give desired yields and molar proportionsof the respective recurring units, y' and y are block lengths as definedabove, n is the total number of recurring units, and x is a molarquantity substantially less than m' that is selected to give anappropriate block length of the first homo-oligomer end-capped witho-diamine functional groups,

The preferred XIV block polymers are those wherein m', m, x, n, y, y'are as defined above, q is equal to m'/m+m' and p is equal to m/2(m+m').

Selected molar quantity, m, of a monomer of Type 1 may be mixed with aphosphoric acid having a phosphorus pentoxide content of from about 63%to about 78%, preferably greater than about 68%, most preferably about78%, and the protecting groups, if present, may be removed as describedpreviously. The quantity of the phosphoric acid is most desirablydetermined in accordance with equation a* as described above. Astoichiometric quantity (i.e., m) of a monomer of Type 2, 4, 6, 7, or 8may then be added to the resulting solution. The phosphorus pentoxidecontent of the resulting mixture may then be raised in accordance withequation b* given above, so as to raise the final phosphorus pentoxidecontent of the substantially polymerized mixture to a value greater thanabout 81%, most preferably between about 82% to about 83.5%, but lessthan about 84%. The resulting mixture may then be heated to about 100°C. to about 185° C., most preferably to about 170° C. to about 185° C.,within a practical period of time, preferably within a period of fromless than about one to about 5 hours, most preferably from about one toabout 3 hours. This temperature is maintained for sufficient time toachieve a selected n value, hereinafter referred to as thehomo-oligomeric n value, that is above a selected minimum value to bedescribed for specific cases below, is characterized as being equal to1/2(1-p), where p is the extent of reaction, defined as the molefraction of either type of functional group present that has undergonecondensation, and being preferrably below a selected maximum valuecharacteristic of complete polymerization. A selected molar quantity,m_(ij), of the homo-oligomeric reaction product thus obtained isdiverted into a second vessel containing a selected molar quantity,m_(ij), of a similarly obtained but structurally differenthomo-oligomeric reaction product and the heating at elevatedtemperatures continued.

The average block lengths, y_(ij), of the block polymers of thecompositions of the present invention may be determined in the followingway. The ijth homo-oligomeric reaction product is prepared by addinga_(i) moles of a first monomer to an equimolar b_(j) of the secondmonomer. The sum of all a_(i) or b_(j) is one. The ijth homo-oligomericreaction product prepared above has, by definition, been polymerized toa selected intermediate extent of reaction, P_(ij). The homo-oligomericn value of the ijth homo-oligomeric reaction product, n_(ij), is givenby 1/2(1-p_(ij)). The molar proportions of the recurring unitsincorporated into the block polymer is given by ##EQU5## The blocklengths y_(ij) may be calculated by the equation ##EQU6## which assumesthat the homo-oligomers condense with equal reactivity. The aboveequation for y_(ij) shows that if either of two homo-oligomeric reactionproducts are polymerized to high conversion, (i.e., allowed to achieve ahigh n_(ij) value before mixing) then both block lengths in theresulting block polymer will be high.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include block polymers withthe general formulas IX, XII, XVI, XVIII, and XIX is illustrated forthose compositions including general formula IX wherein the selectedfirst homo-oligomer may be prepared from monomers of Type 1 and Type 2that are further classified as belonging to Class 1 and the selectedsecond homo-oligomer is further characterized as belonging to eitherClass 1, Class 2, or Class 3.

General formula IX block polymers may be prepared from homo-oligomersderived exclusively from Class 1 monomers. The block polymers,##STR148## have the same advantage of a broad range of operableconcentrations as described for copolymers formed exclusively from Class1 monomers. The advantage to the block polymer procedure described abovefor these polymers is the ability to vary y₁₁ and y₁₂, or y₂₁, or y₂₂essentially independent of the molar proportion a₁ b₁, or a₂ b₂, or a₂b₁, or a₁ b₂ by selecting appropriate extents of reaction for thecorresponding homo-oligomer. For example, y₁₁ may be 20 or greater for abroad range of a₁ b₁ values by increasing the extent of reaction, p₁₁,as the a₁ b₁ value is decreased. y₁₂, y₂₁, or y₂₂ of the above formulasmay be obtained with values from about one to about 75, most preferablyfrom about 25 to about 50, by selecting appropriate p₁₁ and p₁₂, p₂₁, orp₂₂ values. In practice, the members of this selected class of blockpolymers, because all the recurring units have a high degree ofmesogenicity, are liquid-crystalline when an n value of greater thanabout 40 is obtained at a concentration of greater than about 6 weightpercent independent of the block lengths achieved. The practice of theinvention as it relates to block polymers of Class 1 is furtherillustrated in Examples 75-84 below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 2 monomers. The block polymers, ##STR149## arederived from homo-oligomers of different mesogenicity. The selection ofa₁ b₁ (the molar proportion of the first and more highly mesogenicrecurring unit) and the preferred y₁₁ (the average block length of thefirst and more highly mesogenic recurring unit) are governed by thefollowing considerations. The block polymer reaction product is thefirst case may derive liquid-crystalline behavior by virtue of the solepresence of the first recurring unit when y₁₁ is greater than about 30,more preferably greater than about 40, at concentrations of the firstrecurring unit alone (i.e., the weight of the first oligomeradded/weight of the final block polymer reaction product) greater thanabout 7 percent, or the block polymer reaction product in the secondcase may derive liquid-crystalline behavior by virtue of the combinedpresence of both recurring units, independent of y₁₁, at concentrationsabove which the moderately mesogenic recurring unit derived from thesecond homo-oligomer is liquid-crystalline alone. The preferred valuesof a₁ b₁ are from about 0.4 to about one, with y₁₁ ranging from about 80to about 20, respectively, as a₁ b₁ is varied from 0.4 to one. The mostpreferred concentrations of these block polymers is above about 15weight percent but may be lower as either the a₁ b₁ value or the y₁₁value or both values are increased. The preferred n value for thesecompositions is from about 50 to 150, most preferably greater than 100.Obtaining sufficient n values may be aided by the addition of the secondhomo-oligomeric reaction product before the phosphorus pentoxide contentis raised to the value necessary for polymerization (i.e., when p₁₂ orp₂₁ is zero and n₁₂ or n₂₁ =1/2) and then adding the appropriate amountof phosphorus pentoxide to raise the mixture to sufficient phosphoruspentoxide content. This procedure aids in mixing and is most preferredwhen the homo-oligomeric n value of the first homo-oligomer, n₁₁, islarge. The practice of the invention as it relates to the preparation ofblock polymers of Class 2 is further illustrated in Examples 85-88below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 3 monomers. The block polymers ##STR150## derivetheir liquid-crystalline behavior entirely from the presence of thefirst recurring unit, its average block length y₁₁, and itsconcentration alone in the total weight of the final block polymerreaction product. Thus, the values of a₁ b₁, y₁₁, and concentration mustmeet the conditions of the first case described for the block polymerscontaining Class 2 monomers. The method of the invention allows thepreparation of such highly concentrated mixtures of mesogenic units,i.e., reaction products substantially higher in polymer concentrationthan that required for liquid-crystalline behavior, that incorporationof significant amounts of non-mesogenic units is possible if the aboveconditions are met.

The preferred values of a₁ b₁ are from about 0.6 to about one. Thepreferred values of y₁₁ are from at least about 30 to about 100, morepreferably between about 50 to 100. The preferred values of y₁₂ or y₂₁are from about one to about 50. The preferred values of n are from about50 to 200 with the most preferred values being about 100 to 150. Thepreferred selected concentrations of the block polymer are above about15 weight percent, especially as the proportion of the non-mesogenicrecurring unit is increased. The practice of the invention as it relatesto production of block polymers containing Class 3 monomers is furtherillustrated in Examples 73, 74, 89-94 below.

The practice of the invention as it relates to the production of novelliquid-crystalline compositions that include block polymers with thegeneral formulas X, XV, XVII are illustrated for block polymers offormula X wherein the selected first homo-oligomer is prepared from Type(1,1) or (1,2) and Type (2,1) monomers and the selected secondhomo-oligomer is prepared from monomers of Type (3,2).

The general formulas X, XV, and XVII liquid crystalline block polymercompositions shown above are prepared according to the followingprocedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1e) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2e) then increasing the phosphorus pentoxide content of the mixtureresulting from step (1e) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(3e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1e) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomer of step (a) whichforms the first homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, the general formulas X, XV, and XVII liquid crystallineblock polymer compositions shown above may be also prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) mixing a selected amount of the solution of step (b) with a selectedamount of at least one of a selected first homo-oligomeric product so asto form a first oligomeric-first monomer reaction medium, said firsthomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1c) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2c) then increasing the phosporus pentoxide content of the mixtureresulting from step (1) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization.

(3c) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said firsthomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1c) which forms the first monomer solution, be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a reaction medium of greaterphosphorus pentoxide content suitable for polymerization,

(e) causing polymerization of the first oligomer-monomer at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

General formula X block polymers may be derived from a firsthomo-oligomer of Class 1 and a second homo-oligomer of general formula(3,2). The block polymers of Type X are prepared by a procedureanalogous to the procedure described for general formula IX blockpolymers, except that the second homo-oligomer is prepared from a singlemonomer. ##STR151## have preferred molar proportion of the firstrecurring unit, a₁ b₁ m/m+m' of from about zero to about 0.5 when theconcentration selected to be above about 15 weight percent. When a₁ b₁m/m+m' is selected to be above about 0.5 but less than one then theoperable concentration range is extended to include concentration of 7%,more preferably 10 weight percent. At concentrations above about 15weight percent all selected values of y₁₁ and values of y₁ greater thanabout 5 give liquid-crystalline products, but n must be greater thanabout 50, preferably above about 100 to give desirable mechanicalproperties.

The practice of the invention as it relates to the block polymers ofthis Class is further illustrated in Examples 102-112 below

General formula X block polymer may be derived from a firsthomo-oligomer of Class 2 and a second homo-oligomer of Type (3,2). Theblock polymers ##STR152## are prepared from two homo-oligomers of Class2 which dictates the selection of concentrations greater than about 15'weight percent. The molar proportions of the various recurring units areselected based on desired mechanical properties or the maintenance ofsolubility in two recurring units of different solubilitycharacteristics. The preferred values of y₁ are those from about 5-50,more preferably greater than 30. The practice of the invention as itrelates to block polymers of this Class is further illustrated inExamples 113-115 below.

The practice of the invention is illustrated for general formula XI forblock polymers prepared from a single monomer of Type (3,2).

The general formula XI liquid crystalline block polymer compositionsshown above are prepared according to the following procedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a solution of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), and(d) with the overall proviso that at least one of the selected monomerof step (a) which forms the second homo-oligomeric product be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The block polymers ##STR153## have preferred values of c₁ between 0.5and one, owing to the greater solubility and mesogenicity of the firstrecurring unit and preferred values of y₁ greater than about 25 but lessthan about 100, owing to the higher mesogenicity. Concentrations greaterthan about 15%, more preferably greater than about 18%, and mostpreferably 20%, are selected. Examples 98-101 below further illustratethe method of the present invention.

The method of the invention also relates to the preparation of blockpolymers by the condensation of co-oligomeric reaction products, insteadof the homo-oligomeric reaction products described in the aboveprocedures, however these will not be described here for the sake ofsimplicity.

Intrinsic Viscosity

Intrinsic viscosity is determined by extrapolation of η_(rel) -1/c and1n η_(rel) /c to zero concentration in methane sulfonic acid at 30° C.

Anisotropic Character of the Compositions

The extended chain polymer compositions of this invention are opticallyanisotropic, i.e., microscopic regions of a given extended chaincomposition are birefringent; a bulk extended chain composition sampledepolarizes plane-polarized light because the light transmissionproperties of the microscopic areas of the extended chain compositionvary with direction. This characteristic is associated with theexistence of at least part of the extended chain polymer compositions inthe liquid crystalline or mesomorphic state.

The extended chain polymer compositions of this invention that exhibitoptical anisotropy do so while the extended chain polymer compositionsare in the relaxed state. This is in contrast to conventional polymersolutions which may be caused to depolarize plane-polarized light whensubjected to appreciable shear.

The extended chain polymer concentration of the compositions of theinstant invention is above the "critical concentration point." The"critical concentration point" is routinely determined usingconventional concentration and viscosity measuring techniques (seeKwolek U.S. Pat. No. 3,671,542).

Another qualitative determination of the liquid crystalline character ofthese extended chain polymer compositions may be made with the nakedeye. These extended chain polymer compositions may appear turbid or hazyand yet contain no, or practically no undissolved solid. When theextended chain polymer compositions, seen under reflected ordinarylight, is disturbed by shaking or rolling the vessel containing theextended chain polymer compositions or by only slow stirring, there isproduced a characteristic, readily observed, satin-like sheen or glowwhich is observed even after the disturbance ceases, and which decreasesin intensity thereafter. This may be described as being a pearly oropalescent quality of the extended chain polymer compositions of thisinvention. Compositions which are disturbed as described above oftengive the appearance of having striations and/or graininess in thesurface. These visual effects are observed in the liquid crystallineextended chain polymer compositions of this invention. This may commonlybe referred to as "stir opalescence." Further details on qualitative andquantitative determinations of optical anisotropy are presented inKwolek U.S. Pat. No. 3,671,542.

Fiber Preparation

The liquid crystalline compositions may be formed into fibers of highquality by spinning them into suitable baths such as by wet and "airgap" spinning techniques, using spinnerets and other apparatusconstructed of materials resistant to the strong acids used. In"air-gap" spinning the spinneret is usually located in air or in aninert gaseous medium a short distance (e.g., 1 to 24 cm) above thesurface of a coagulating bath.

However, air-gaps suitable for use in the present invention may rangefrom less than about 1 cm to about 150 cm or longer, preferably fromabout 2 cm to about 300 cm, more preferably from about 10 cm to about200 cm, and most preferably from about 10 cm to about 100 cm.

In the present invention, the initial draw ratio is approximately fromabout 1:1 to about 50:1 and higher. Preferably, the initial draw ratiois from about 20:1 to about 80:1, especially preferably, from about 60:1to about 200:1, and, most preferably, from about 100:1 to about 150:1.

The term "draw ratio", as is well known, is a measure of the degree ofstretching during the orientation of the fibrous material. In thepresent invention, the initial draw ratio is a measure of the degree ofstretching of the filaments which occurs between the extrusion orificesand the exit from the coagulation bath. The initial draw ratio isdefined as exit velocity divided by jet speed.

The jet speed is the speed at which the extruded polymer exits anextrusion orifice. It is conveniently determined by dividing the totalpolymer extrusion velocity by the total surface area of the extrusionorifices.

The exit velocity is the speed at which the filaments leave thecoagulation bath. Although any means of measurement may be used, theexit velocity is conveniently determined by the surface speed of therolls which take up the filaments after their exit from the bath. Thus,the speed of the wash rolls is preferably measured for this purpose.

Spinning of polybenzimidazole fibers by one working of this generaltechnique is described in, e.g., Tan U.S. Pat. No. 4,263,245. A varietyof baths may be used to coagulate the extruded dope into fibers. Thebaths may be, e.g., water or methanol and the like, or a dilute solutionof a mineral acid (for example, phosphoric acid or sulfuric acid and thelike). Preferably, the temperature of a coagulation bath is roomtemperature or below.

It is desirable to completely remove the spinning solvent from fibersamples prepared from the liquid crystalline compositions of thisinvention. Water alone or aqueous alkaline solutions may be used forremoval of the residual acid. A convenient method is to spray thethreadline as it leaves the coagulating bath with an aqueous alkalinesolution (e.g., saturated sodium bicarbonate), remove the surface liquidfrom the threadline with a wiping device (e.g., a sponge) or a jet, washwith water and/or aqueous alkaline solutions to reduce the acid content,and wind up the fibers on bobbins. The fibers may be soaked in water fora period sufficient to remove the acid. The thoroughly washed fibers maybe dried on the bobbin in the area of temperatures of up to about 110°C. They can also be conveniently dried on heated rolls.

The liquid crystalline compositions are especially suitable forextruding. This and other methods of article frabication are fullydescribed in J. S. Robinson, "Spinning, Extruding, and Processing ofFibers"; Chemical Technology Review No. 159, Noyes Data Corp., 1980. Theabove cited patents and/or publications are incorporated herein byreference.

The fibers prepared from the polymers of this invention exhibit highvalues of tensile properties, especially in the as-extruded state, i.e.,without subsequent hot drawing or annealing. The tensile properties ofthese as-extruded fibers can be enhanced by subjecting the undrawnfibers to a heat treatment. Fiber tensile properties.

Filament properties are measured on fibers that are conditioned at 21degrees C. and 65% relative humidity (R.H.) for at least 16 hours unlessotherwise specified. Yarn properties are measured on yarn that areconditioned at 24 degrees C. and 55% R.H. for at least 16 hours. Allmeasurements are made in the fiber conditioning environment.

Tenacity (breaking tenacity) (T), elongation (breaking elongation( (E),and initial modulus (Mi) are obtained from breaking a single filament ora multifilament yarn on an Instron tester (Instron Engineering Corp.,Canton, Mass.).

Single filaments are broken with a gage length (distance between jaws)of 1.0 inch (2.54 cm.). The results on 3 filaments are averaged. Yarnsare given 3 turns per inch (2.54 cm.) twist (under 0.1 g.p.d. tension)and broken with a 10 inch (25.4 cm.) gage length. All samples areelongated at a constant rate of extension (10% elongation/minute forfibers having an E of under 8%, and 60% elongation/minute for fiberswith E of 8 to 100%) until the sample breaks.

The denier of a single filament (d.p.f.) is calculated from itsfunctional resonant frequency, determined by vibrating a 7 to 9 cm.length of fiber under tension with changing frequency (ASTM D1577-1973).This filament is then used for 1 break.

The denier of yarn is determined by weighing a known length (at 0.1g.p.d. tension); 90 cm. length is convenient.

The tenacity (grams/denier), elongation (percent) and initial modulus(gram/denier) as defined in ASTM 3379-75e are obtained from theload-elongation curve and the measured denier. In actual practice, themeasured denier of the sample, test conditions and sample identificationmaybe fed to a computer before the start of a test; the computer recordthe load-elongation curve of the fiber as it is broken and thencalculates the fiber properties.

It should be noted that different values maybe obtained from singlefilaments (filament properties) and from multifilament strands (yarnproperties) of the same sample. Unless specified otherwise allproperties mentioned herein are filament properties.

Additives

It will be understood that the usual additives such as dyes, fillers,antioxidants, and the like can be incorporated into the compositions ofthe present invention for the purpose intended, before preparation ofthe shaped article.

Mineral acids that are solvents for the extended chain polymers of theinstant compositions such as polyphosphoric acid, methane sulfonic acid,100% sulfuric acid, chlorosulfonic acid, and the like, may be added tothe compositions of the invention in minor amounts (without departingfrom the scope of the invention) for purposes of modifying conditionsfor processing into shaped articles. The strong acid additives maycontain one or more of the acid-soluble polymers described in Helmimiak,et. al., U.S. Pat. No. 4,207,407 and P. D. Sybert, "Rigid-RodPolyquinolines: Synthesis, Structure-Property Relationships andHigh-Strength Fibers", Colorado State University, Ph.D. Thesis, 1980.The above cited patent and thesis are incorporated herein by reference.4. Industrial Applicability

The liquid crystalline extended chain polymer compositions are extremelysuitable for spinning into highly ordered and high strength fibers. Suchfibers are useful substitutes for other inorganic or organicreinforcement products. Various examples include glass fibers, asbestos,boron fibers, carbon and graphite fibers, whiskers, quartz and silicafibers, ceramic fibers, metal fibers, natural organic fibers, andsynthetic organic fibers. A reinforcement may be defined simply as thematerial that is added to a resinous matrix to improve the strength andother physical and chemical properties of the material.

Furthermore, the polymers of the instant compositions can be employed inany use typically performed by engineering thermoplastic materials, suchas metal replacements and those areas where high performance isnecessary. Extended chain polymer compositions may be employed for usein forming high strength films suitable in the production of composites,belts, tires, i.e., as tire cords, and the like. The films are suitableas construction materials for rocket nose cones and various other partsof space craft.

Depending on the extended chain polymer fiber or films selected (i.e.,homopolymer, copolymer, block polymer, or mixture thereof) theproperties of the article formed may be controlled to suit the desireduse. The control of polymer properties is an advantage, since, in thevarious areas of utility for such polymers, e.g. as laminates,structural materials, adhesives and ablative materials, the needs varyconsiderably.

By way of comparison, Examples 1-5 below are illustrative of lowmolecular weight (i.e., low intrinsic viscosity) and/or low polymerconcentration compositions.

EXAMPLE 1

In a 6-L resin flask were placed 386.76 g (1.5774 mol) of2,5-diamino-1,4-benzenedithiol dihydrochloride (1a) and 2.98 kg offreshly prepared PPA. The PPA was prepared as described in Wolfe andArnold, Macromolecules, Vol 14, 909 (1981). The mixture was stirred atroom temperature under a flow of argon for 24h and heated at 60°-70° C.for 34h. The resulting solution was clear with no evidence of bubbles.Terephthalic acid (262.35 g, 1,5792 mol) was then added and incorporatedinto the solution by rapid stirring at 110° C. Additional PPA (4.1 kg)was then added. The yellow mixture was heated as follows: 110°-165° C.in 5h, 165° C. for 12h, 180° C. for 12h, and 195° C. for 12h. Themixture became stir-opalescent after 6h at polymerization temperatures.Reduced pressure was applied during the first 6h of reaction but wasalternated with an argon stream such that the mixture did not foam abovea predetermined flask wall level. The hazy green product exhibitingyellow-green opalescence was removed from the flask and precipitatedinto a large volume of water. The copper-colored polymer was washeduntil the water was no longer acidic and then dried at 80°-100° C. underreduced pressure for 48h. A portion of the reaction product was bottledfor use in fiber-spinning studies: intrinsic viscosity [η]=30.3 dL/g(MSA). Anal.Calcd for C₁₄ H₆ N₂ S₂ : C,63.13; H,2.27; N,10.51; S,24.08.Found: C,62.75; H, 2.346; N, 10.24; S, 23.22. The foregoing procedureprovided a 5.6 wt % of polymer --AI]_(n) in PPA. Polymerization mixturesof higher polymer concentration (up to 10%) were prepared. These runsrequired higher monomer 1a concentration during dehydrochlorination.Intermittent cooling was cycled with argon pressure as required tocontrol foaming at the desired level in the reaction vessel. Similarly,polymer --AI]_(n) in PPA of lower concentration were prepared and theserequired less time for complete dehydrochlorination than that described.

EXAMPLE 2

In a 6-L resin flask were placed 919.94 g (3.7519 mol) of 1a andapproximately 2.7 kg of 115% PPA. The 115% PPA was obtained from FMCCorporation and heated to 150° C. under an argon atmosphere, heated at150° C. under reduced pressure for 18h, and cooled to room temperatureimmediately before use. The viscous mixture was stirred and an ice bathwas applied for 24h to prevent vigorous foaming. Five additional days ofstirring at room temperature were required to remove enough hydrogenchloride to allow heating above room temperature. A clear, viscoussolution was obtained after heating for 18h at 80° C. Finely powdered 2a(622.90 g, 3.7454 mol) and an additional 2.773 g of the above 115% PPAwere then added. The mixture was then stirred and heated to 140° C. for3h and then heated at 150°-160° C. for 16h. The mixture graduallydarkened, became optically isotropic, and never became noticeably moreviscous. Samples that were removed and precipitated in water gave a darkgreen non-fibrous material. Additional heating failed to increase theviscosity to an extent to yield a fibrous material. The theoreticalpolymer concentration --AI] for this experiment was 14.8% in a PPA withan intermediate P₂ O₅ content of 83.8% and a final of 79.8%.

EXAMPLE 3

To a 100 mL flask containing 15.8 g of concentrated orthophosphoric acid(85.4% H₃ PO₄) that had been cooled in an ice bath was added 24.2 g ofphosphorus pentoxide and the mixture heated at 150° C. for 6h under anargon atmosphere. After cooling the PPA (84.9% P₂ O₅) to roomtemperature, 6.0 g (0.029 mol) of 4-amino-3-mercaptobenzoic acidhydrochloride (3a) (prepared by the method of Wolfe, AFOSR FinalTechnical Report, Dec. 15, 1980) was added and the viscous mixturestirred at 40° C. for 24h. The mixture was then placed under reducedpressure and the temperature slowly raised to 70° C. The orangeyellowmixture was then heated to 150° C. over a 2h period. The resulting darkred solution was optically isotropic. The solution was then stirred at150° C. for an additional 24h. The polymer was isolated from theresulting optically isotropic solution containing 8.6% of the polymer byprecipitation with water to give brittle films. The intrinsic viscosityof the isolated polymer --T]_(n) was 3.0 dL/g in methanesulfonic acid at30° C.

EXAMPLE 4

To a 50 mL round bottom flask containing 48.15 g of PPA that wasprepared as described in Wolfe and Arnold, Macromolecules, Vol. 14, 909(1981) was added 7.436 g (0.03616 mol) of 4-amino-3-mercaptobenzoic acidhydrochloride (3a) that was prepared as described in Wolfe, AFOSR FinalTechnical Report, Dec. 15, 1980. The mixture was stirred at roomtemperature under an argon flow for 18h. After stirring for 2h underreduced pressure between 50° to 80° C. the solution was a clear orangecolor. The solution was then heated under reduced pressure as follows:90° C. for 0.5h; 100° C. for 0.5h; 110° C. for 0.5h; 130° C. for 0.5h;140° C. for 0.5h; 180° C. for 8h; 150° C. for 5h; 190° C. for 16h; 160°C. for 16h; 160° C. for 16h; 200° C. for 200h and 170° C. for 7h. Theresulting isotropic solution having a concentration of polymer --T]_(n)of 9.4% by weight gave only brittle amorphous films when precipitated inwater. The intrinsic viscosity of the isolated polymer was 3.80 dL/g inmethanesulfonic acid at 30.0° C.

EXAMPLE 5

To 38 g of PPA that was prepared as described in Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981) was added 1.421 g (8.41 mmol) of4-amino-3-mercaptobenzoic acid (3b) that was prepared by neutralizationof an aqueous suspension of 4-amino-3-mercaptobenzoic acid hydrochloride(3a) (prepared according to Wolfe, AFOSR Final Technical Report, Dec.15, 1980) followed by extraction with ethyl acetate, evaporation of theethyl acetate, and recrystallization of the pale yellow residue frommethylene chloride. The viscous mixture was heated to 140° C. under anargon flow in a 0.5h period. The temperature was raised to 160° C. overa 0.5h period and then maintained at 160° C. for 18h under reducedpressure. The optically isotropic, red solution was then heated underreduced pressure for 8h at 200° C. The isolated polymer --T]_(n) had anintrinsic viscosity of 4.57 dL/g in MSA at 30.0° C.

The compositions of this invention, their production and theiradvantages and uses are further illustrated in the following examples.These are intended only to demonstrate the invention and are not to beconstrued as limiting its scope, which scope is instead defined by theappended claims.

All polyphosphoric acid (PPA) hereinafter referred to as 115% wasobtained from FMC Corporation and used as received. Terephthalic acid(2a) was obtained from Amoco Chemicals Company, reduced to an averageparticle size of 95% <10 μm by an air-impact method, and dried beforeuse. All monomers and P₂ O₅ that were added to PPA were deaerated byplacing them in a desiccator, applying reduced pressure, filling with aninert gas, and repeating the procedure at least once.

EXAMPLE 6

A mixture of 88.2 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 205.2 g of 115% PPA was stirred at 100° C. for 2h under reducedpressure. After allowing the PPA solution to cool to approximately 50°C. a portion of this solution (282.1 g) was added to a 500 mL resinkettle containing 53.01013 g (0.21620 mol) of 1a. After stirring toincorporate the solid monomer into the PPA, the mixture was stirred atroom temperature for 2h under argon and then under reduced pressure at:25°-30° C. for 24h; 50° C. for 3h; and 70° C. for 16h. Monomer 2a(35.91734 g, 0.216196 mol) was then added to the resulting clear lightgreen soltion in four portions. After the addition of each portion, thereaction kettle was placed under reduced pressure before the 2a wasincorporated by stirring. The mixture was allowed to cool toapproximately 50° C. before 118.3 g of P₂ O₅ was added to increase theeffective P₂ O₅ content to 83.9%. The viscous slurry was then heated asfollows: 100°-170° C. in 3h; 170° C. for 17h; 185° C. for 5h; and 200°C. for 19h. The intrinsic viscosities (in dL/g) of the polymer --AI]_(n)were determined from samples of the polymer solution withdrawn at thepolymerization times indicated: 9.2 (8.5h), 12.6 (25.5h), 15.8 (44.0h).Heating this reaction solution at 200° C. for an additional 76h onlyincreased the intrinsic viscosity of the --AI]_(n) component to 16.4dL/g. The reaction product is characterized as having a final P₂ O₅content of approximately 80.8% with the --AI]_(n) polymer concentrationbeing approximately 12.6 wt %.

EXAMPLE 7

A mixture of 57.3 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 133.7 g of 115% PPA was stirred at 100° C. for 4h under reducedpressure. After allowing the PPA solution to cool to room temperature, aportion of this solution (185.0 g) was added to a 500 mL resin kettlecontaining 53.61422 g (0.21866 mol) of 1a. (Monomer 1a of small crystalsize was prepared without a final recrystallization according to themethod of Wolfe, Loo, and Arnold, Macromolecules Vol. 14, 915 (1981)using the final isolation procedure involving the transfer of thedipotassium salt of 1a as an aqueous solution into 6N hydrochloricacid.) After stirring to incorporate the monomer into the PPA, themixture was stirred at 55°-65° C. for 5.5h under reduced pressure, at25° C. for 15.5h under an argon flow, and at 65°-72° C. for 4h underreduced pressure. Monomer 2a (36.3268 g), 0.21866 mol) was added to theresin kettle cotaining the dehydrochlorinated solution of monomer 1a inPPA. After the addition of each of the six portions, the incorporationof the solid into the solution was aided by placing the kettle underreduced pressure before stirring was initiated. Powdered phosphoruspentoxide (114.4 g) was then added to increase the effective P₂ O₅content to 86.4% and the mixture was stirred at 100° C. for 27h. Thepolymerization mixture was then heated as follows: 100°-170° C. in 1h;170° C. for 21.5h; and 200° C. for 71.5h. The intrinsic viscosities (indL/g) of the polymer --AL]_(n) were determined from samples withdrawn atthe polymerization times indicated: 23.1 (22.5h), 24.8 (29.0h), 27.0(94h). The reaction product is characterized as having a final effectiveP₂ O₅ content of approximately 82.2% and a polymer --AI]_(n)concentration being approximately 15.2 wt %.

EXAMPLE 8

182.7 g of a PPA solution with an effective P₂ O₅ content of 77.2%(prepared by mixing 30 wt % of H₃ PO₄ and 70 wt % of 115% PPA) was addedto a 500 mL resin kettle containing 52.62853 g (0.21460 mol) of 1a.(Monomer 1a of large crystal size was prepared with a finalrecrystallization according to the method of Wolfe, Loo, and Arnold,Macromolecules, 14, 915 (1981) using the final isolation procedureinvolving a transfer of the dipotassium salt of monomer 1a as solid into6N hydrochloric acid.) After stirring to incorporate the solid monomerinto the PPA, the mixture was substantially dehydrochlorinated byheating the mixture at 55°-70° C. under reduced pressure forapproximately 31h. Monomer 2a (35.6522 g, 0.21460 mol) was added to theresin kettle and incorporated as described in the previous Example.Powdered P₂ O₅ (123.35 g) was then added to increase the effective P₂ O₅content to approximately 86.4% and resulting mixture was stirred at 100°C. for 17h under an argon flow. The polymerization mixture was thenheated with stirring as follows: 100°-170° C. in 1h, 170° C. for 23h,and 200° C. for 24h. The intrinsic viscosities (in dL/g) were determinedfor the --AI]_(n) polymer from samples withdrawn at the indicated times:17.2 (7h), 22.8 (24h), and 35.4 (48h). Heating without stirrig for anadditional 24h did not increase the intrinsic viscosity of the --AI]_(n)polymer. The green reaction product exhibits stir-opalescence and ischaracterized as having a final effective P₂ O₅ content of 82.2% with--AI]_(n) polymer concentration being approximately 15.1 wt %.

EXAMPLE 9

A mixture of 4,925 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 11.491 g of 115% PPA was stirred in a 22 L flask for 5h at 100° C.under reduced pressure. After allowing the PPA solution to cool to 50°C. under a flow of argon, a portion of this solution (11,321 g) wasadded to a 40-L glass resin kettle (equipped with a mechanical stirrerconsisting of a 3/4 hp variable speed drive and stirring blades made ofHastelloy C-276) containing 2,380.55 g (9.7088 mol) of 1a prepared asdescribed in Example 7. The mixture was then stirred at: 65° C. for 17hunder a flow of argon; 65° C. for 2h at 700-400 mm Hg; and 65° C. for 2hat 40 mm Hg. An additional 2,552.77 g (10.4112 mol) of monomer 1a thathad been prepared and deaerated as described in Example 8 was then addedunder a flow of argon. An additional 4,874 g of the above-mentioned PPAwas added and the mixture stirred at: 65° C. for 1h at 700-300 mm Hg;65°-70° C. for 3.25h at 40 mm Hg; 70° C. for 2.5h at less than 5 mm Hg;700° C. for 7.5h under a flow of argon; and 80° C. for 26h at less than5 mm Hg. Monomer 2a (3,342.62 g, 20.1205 mol) was then added. Theresulting slurry was then cooled to 40° C. and 6,512.1 g of powdered P₂O₅ was added over a 4.5 period. The resulting viscous mixture wasstirred at 80° C. for 17h under an argon flow. The mixture was thenheated to 100° C. and an additional 4,655.4 g of P₂ O₅ was added toincrease the effective P₂ O.sub. 5 content to 86.5%. After stirring foran additional 48h at 100°-108° C., the polymerization mixture was heatedas follows: 100°-170° C. in 3h; 170° C. for 20h; and 200° C. for 1.5h.The intrinsic viscosities (in dL/g) were determined from sampleswithdrawn at the indicated reaction times: 17.9 (14h), 18.5 (16.5h),19.0 (23h), 24.34 (24.5h). Additional heating at 200° C. only increasedthe intrinsic viscosity to 24.6 dL/g. The reaction product exhibitedstir-opalescence and is characterized as having a final effective P₂ O₅content of 82.2% with the --AI]_(n) polymer concentration beingapproximately 15.6% by weight.

EXAMPLE 10

To a 500 mL resin kettle containing a deaerated mixture of 12.06155 g(0.0594092 mol) of terephthaloyl chloride (2b) and 14.5665 g (0.0594081mol) of 1a was added approximately 140 g of 115% PPA that had beenstirred at 100° C. under reduced pressure for 1-2h, and had cooled toroom temperature. The mixture was then stirred under an argon flow at:40° C. for 23h; 50° C. for 3h; 60° C. for 2h; 70° C. for 19h; and 80° C.for 3h. The solution was then stirred at 80° C. under reduced pressurefor 1h. An additional 140 g of deaerated 115% PPA was then incorporatedinto the solution. The polymerization was stirred under argon at: 100°C. for 30 min; 110° C. for 30 min; 120° C. for 30 min; 130° C. for 30min; 140° C. for 30 min; 150° C. for 30 min; 160° C. for 45 min; 170° C.for 11h; 185° C. for 5h; and 200° C. for 46.5h. Precipitation in waterof a small amount of the anisotropic product provided polymer --AI]_(n)which possessed an intrinsic viscosity of 17.7 (dL/g) in MSA at 30° C.

EXAMPLE 11

A mixture of 74.52 g of 85.7% orthophosphoric acid and 173.88 g of 115%PPA (83.8% P₂ O₅ content) is stirred under reduced pressure for 2h at100° C. After cooling to room temperature, 55.23561 g (0.225273 mol) of1a (prepared as described in Example 8) and 45.73607 g (0.225273 mol) of2b (freshly sublimed) are added in eight portions. After the addition ofeach portion of monomer stirring is initiated to incorporate themonomer. The mixture is then stirred while the temperature is slowlyincreased and the pressure is slowly decreased until dehydrochlorinationis complete. Deaerated phosphorus pentoxide (87.54 g) is then added tothe dehydrochlorination mixture at 50° C. The mixture is then stirred at100° C. for several hours. The polymerization is then stirred under anargon atmosphere at 170° C. for approximately 20h, at 180° C. forapproximately 8h, and at 200° C. for 3h. The resulting product contains15 wt % of --AI]_(n) in PPA (82.2% P₂ O₅).

EXAMPLE 12

86.17 g of a PPA solution with an effective P₂ O₅ content of 74.9%(prepared by mixing 40 wt % of 85% H₃ PO₄ and 60 wt % of 115% PPA) wasadded to a 500 mL resin kettle containing 27.62485 g (0.112665 mol) of1a. The monomer was incorporated into the PPA solution by stirring andthe resulting mixture was then substantially dehydrochlorinated byheating the mixture at 55°-80° C. under reduced pressure forapproximately 21h. Monomer 2a (18.7208g, 0.112686 mol) was then added tothe resin kettle. Powdered P₂ O₅ (83.17 g) was then added to increasethe effective P₂ O₅ content to approximately 87.2%. The resulting yellowslurry was stirred at 100° C. for 15h under an argon flow. This slurry,which had not noticeably increased in bulk viscosity, was then stirredvigorously and heated by increasing the oil bath temperature from 100°C. to 178° C. within 40 minutes, and to 185° C. within 1h.Polymerization times indicated below begin with time above 100° C. The185° C. temperature was then maintained for 76.5h. Intrinsic viscositiesin MSA at 30° C. (in dL/g) were determined for the --AI]_(n) polymerfrom samples withdrawn at the indicated polymerization times: 16.6(1.5h), 21.7 (2.25h), 24.2 (3.25h), 35.7 (7.7h), and 42.1 (76.5h). Theintrinsic viscosity of 42.1 corresponds to an average n value ofpolymerization of about 140. The polymerization product wasstir-opalescent after a polymerization time of 0.75h and was found to behighly drawable after 1.25h. Fibers prepared by directly drawing thisproduct and precipitating the strands into water were amber,translucent, birefringent (crossed polars), showed extinction oftransmitted light when a single polaroid sheet was placed perpendicularto the fiber direction, and could be fibrillated into microfibrils.Fibers prepared after 1.5h by the same method were noticeably strongerthan the sample at 1.25h. The bulk viscosity of the product and therelaxation time of opalescence had noticeably increased after 2.25h. TheP₂ O₅ content of the PPA component of the product was approximately83.2% and the concentration of the --AI]_(n) polymer was 14.5% by weightbased on the total weight of the resulting reaction product.

EXAMPLE 13

A mixture of 17.7 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 26.6 g of 115% PPA was stirred under reduced pressure at 100° C. for2h. The resulting solution was then poured at approximately 100° C.under a stream of argon into a 200 mL resin kettle containing 11.41145 g(0.054028 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981), recrystallized from aqueoushydrochloric acid containing 3 wt % stannous chloride, and dried for 20hat 63° C. under reduced pressure immediately before use. The mixture wasstirred at 53° C. for 15h and 62° C. for 4h under reduced pressure. Uponheating to 70° C., the monomer precipitated. Addition of 16.6 g of P₂ O₅resulted in redissolution of the monomer. The solution was then heatedat 100° C. for 3h under reduced pressure to complete thedehydrochlorination. Monomer 2a (8.9761 g, 0.05403 mol) was then addedunder an argon flow. Additional P₂ O₅ (19.0 g) was then added. Thesolution was then heated as follows: 100° C. for 48h; 150° C. for 2.5h;160° C. for 10h (the dark green solution became stiropalescent duringthis period); and 180° C. for 25h. The resulting reaction product wasdeep purple with a metallic luster, exhibited stiropalescence,depolarized plane-polarized light as evidenced by strong birefringencewhen viewed between crossed polars, and is further characterized ashavng a final effective P₂ O₅ content of 82% with the --BI]_(n) polymerconcentration being 13.3% by weight. The intrinsic viscosity of thepolymer --BI]_(n) isolated from the reaction product was 23.9 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 110.

EXAMPLE 14

The reaction product from Example 13 was drawn many times its length togive highly fibrillar fibers. A portion of the solution was removed fromthe reaction flask and placed in a KBr press equipped with a die with acircular orifice of 0.13 mm in diameter. The solution was extruded intothe air and stretched by pulling manually and then the fiber was dippedin water. The fiber thus produced was washed with water and then driedunder tension in an air oven overnight at 110° C. The fiber produced wasmeasured to be between 0.0093 mm and 0.012 mm in diameter. Highorientation was evident from fibrils which split from the surface of thefiber and by the complete extinction of light transmitted through thefiber when a single polaroid was placed in a perpendicular directiononly between the source and the fiber.

EXAMPLE 15

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 48.9831 g (0.19978 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 269.68 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 80.9 g of 85.4% H₃ PO₄ with 188.8 g of 115% PPA).When dehydrochlorination is substantially complete, 79.9805 g (0.19978mol) of monomer 2s is added followed by the gradual addition of 142.23 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 85.07%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 19%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AIBI].sub.n

characterized by an intrinsic viscosity of 20 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 50.

EXAMPLE 16

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 64.4470 g (0.26284 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 341.97 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 102.6 g of 85.4% H₃ PO₄ with 239.4 g of 115% PPA).When dehydrochlorination is substantially complete, 63.6826 g (0.26284mol) of monomer 2j is added followed by the gradual addition of 137.3 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --A].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 100.

EXAMPLE 17

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 61.1619 g (0.28706 mol) of monomer 1b is dehydrochlorinatedin an "initial" solution of 338.4 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 101.5 g of 85.4% H₃ PO₄ with 236.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.5488 g (0.28706mol) of monomer 2j is added followed by the gradual addition of 140.1 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AB].sub.n

characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization fo about 60.

EXAMPLE 18

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 81.9923 g (0.28869 mol) of monomer 1c is dehydrochlorinatedin an "initial" solution of 366.8 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 110 g of 85.4% H₃ PO₄ with 256.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.9438 g (0.28869mol) of monomer 2j is added followed by the gradual addition of 148.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 16%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AC].sub.n

characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 60.

EXAMPLE 19

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.8232 g (0.29202 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 350.1 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 105 g of 85.4% H₃ PO₄ with 245 g of 115% PPA). Whendehydrochlorination is substantially complete, 48.5129 g (0.29202 mol)of monomer 2a is added followed by the gradual addition of 195.5 g of P₂O₅. The mixture is then stirred and heated essentially according toExample 8. The amount of P₂ O₅ is preselected (as determined in accordwith the aforementioned formulae a* and b*) to provide the reactionmixture with an effective P₂ O₅ content of approximately 85.3% prior tothe start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --LI].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 20

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 340.5 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 102.16 g of 85.4% H₃ PO₄ with 238.4 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added followed by the gradual addition of 202.9 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 85.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --MI].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 21

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 340.5 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 102.16 g of 85.4% H₃ PO₄ with 238.4 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added followed by the gradual addition of 202.9 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 85.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --NI].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 22

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 128.4748 g (0.32431 mol) of monomer 1l is dehydrochlorinatedin an "initial" solution of 288.65 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 86.59 g of 85.4% H₃ PO₄ with 202.05 g of 115% PPA).When dehydrochlorination is substantially complete, 53.8778 g (0.32431mol) of monomer 2a is added followed by the gradual addition of 242.96 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 87.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --OI].sub.n

characterized by an intrinsic viscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 23

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.3707 g (0.21902 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 348.5 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 104.5 g of 85.4% H₃ PO₄ with 132.28 g of 115% PPA).When dehydrochlorination is substantially complete, 53.0654 g (0.21902mol) of monomer 2j is added followed by the gradual addition of 132.28 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.5%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AL].sub.n

characterized by an intrinsic viscosity of 17 dL/g in MSA at 30° C.

EXAMPLE 24

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 315.58 g PPA having a P₂ O₅ content of 75.0%(prepared by mixing 126.23 g of 85.4% H₃ PO₄ with 189.3 g of 164.6% PPA.When dehydrochlorination is substantially complete, 57.0824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 164.6 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AM].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 25

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 315.58 g PPA having a P₂ O₅ content of 75.0%(prepared by mixing 126.23 g of 85.4% H₃ PO₄ with 189.3 g of 115% PPA).When dehydrochlorination is substantially complete, 57.0824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 164.6 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AN].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 6-25, other Type I extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 16a, 16b,17a, 17b, and 17c. The m→, e→, and p→ denote most preferred, especiallypreferred, and preferred selected monomer reactions respectively.

                  TABLE 16a                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR154##                                                                    ##STR155##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR156##                                                                           Polymer I(1)                              ______________________________________                                        1a        +     2e                                                                                         ##STR157##                                                                          [AJ].sub.n                                 1a        +     2f                                                                                         ##STR158##                                                                          [AJ].sub.n                                 1a        +     2i                                                                                         ##STR159##                                                                          [AK].sub.n                                 1a        +     2k                                                                                         ##STR160##                                                                          [AB].sub.n                                 1a        +     2l                                                                                         ##STR161##                                                                          [AC].sub.n                                 1a        +     2m                                                                                         ##STR162##                                                                          [AD].sub.n                                 1a        +     2n                                                                                         ##STR163##                                                                          [AE].sub.n                                 1a        +     2o                                                                                         ##STR164##                                                                          [AF].sub.n                                 1a        +     2p                                                                                         ##STR165##                                                                          [AG].sub.n                                 1a        +     2q                                                                                         ##STR166##                                                                          [AH].sub.n                                 1a        +     2t                                                                                         ##STR167##                                                                          [AICI].sub.n                               1a        +     2u                                                                                         ##STR168##                                                                          [AIDI].sub.n                               1a        +     2v                                                                                         ##STR169##                                                                          [AIEI].sub.n                               1a        +     2w                                                                                         ##STR170##                                                                          [AIFI].sub.n                               1a        +     2x                                                                                         ##STR171##                                                                          [AIGI].sub.n                               1a        +     2y                                                                                         ##STR172##                                                                          [AIHI].sub.n                               1b        +     2e                                                                                         ##STR173##                                                                          [BJ].sub.n                                 1b        +     2i                                                                                         ##STR174##                                                                          [BK].sub.n                                 1b        +     2k                                                                                         ##STR175##                                                                          [B].sub.n                                  1b        +     2l                                                                                         ##STR176##                                                                          [BC].sub.n                                 1b        +     2m                                                                                         ##STR177##                                                                          [BD].sub.n                                 1b        +     2n                                                                                         ##STR178##                                                                          [BE].sub.n                                 1b        +     2o                                                                                         ##STR179##                                                                          [BF].sub.n                                 1b        +     2p                                                                                         ##STR180##                                                                          [BG].sub.n                                 1b        +     2q                                                                                         ##STR181##                                                                          [BH].sub.n                                 1b        +     2t                                                                                         ##STR182##                                                                          [BICI].sub.n                               1b        +     2u                                                                                         ##STR183##                                                                          [BIDI] .sub.n                              1b        +     2v                                                                                         ##STR184##                                                                          [BIEI].sub.n                               1b        +     2w                                                                                         ##STR185##                                                                          [BIFI].sub.n                               1b        +     2x                                                                                         ##STR186##                                                                          [BIGI].sub.n                               1b        +     2y                                                                                         ##STR187##                                                                          [BIHI].sub.n                               1c        +     2a                                                                                         ##STR188##                                                                          [CI].sub.n                                 1c        +     2e                                                                                         ##STR189##                                                                          [CJ].sub.n                                 1c        +     2i                                                                                         ##STR190##                                                                          [CK].sub.n                                 1c        +     2k                                                                                         ##STR191##                                                                          [BC].sub.n                                 1c        +     2l                                                                                         ##STR192##                                                                          [C].sub.n                                  1c        +     2m                                                                                         ##STR193##                                                                          [CD].sub.n                                 1c        +     2n                                                                                         ##STR194##                                                                          [CE].sub.n                                 1c        +     2o                                                                                         ##STR195##                                                                          [CF].sub.n                                 1c        +     2p                                                                                         ##STR196##                                                                          [CG].sub.n                                 1c        +     2q                                                                                         ##STR197##                                                                          [CH].sub.n                                 1c        +     2u                                                                                         ##STR198##                                                                          [CIDI].sub.n                               1c        +     2v                                                                                         ##STR199##                                                                          [CIEI].sub.n                               1c        +     2w                                                                                         ##STR200##                                                                          [CIFI].sub.n                               1c        +     2x                                                                                         ##STR201##                                                                          [CIGI].sub.n                               1c        +     2y                                                                                         ##STR202##                                                                          [CIHI].sub.n                               1d        +     2a                                                                                         ##STR203##                                                                          [DI].sub.n                                 1d        +     2e                                                                                         ##STR204##                                                                          [DJ].sub.n                                 1d        +     2i                                                                                         ##STR205##                                                                          [DK].sub.n                                 1d        +     2m                                                                                         ##STR206##                                                                          [D].sub.n                                  1d        +     2n                                                                                         ##STR207##                                                                          [DE].sub.n                                 1d        +     2o                                                                                         ##STR208##                                                                          [DF].sub.n                                 1d        +     2p                                                                                         ##STR209##                                                                          [DG].sub.n                                 1d        +     2q                                                                                         ##STR210##                                                                          [DH].sub.n                                 1d        +     2v                                                                                         ##STR211##                                                                          [DIEI].sub.n                               1d        +     2w                                                                                         ##STR212##                                                                          [DIFI].sub.n                               1d        +     2x                                                                                         ##STR213##                                                                          [DIGI].sub.n                               1d        +     2y                                                                                         ##STR214##                                                                          [DIHI].sub.n                               1e        +     2a                                                                                         ##STR215##                                                                          [EI].sub.n                                 1e        +     2e                                                                                         ##STR216##                                                                          [EJ].sub.n                                 1e        +     2i                                                                                         ##STR217##                                                                          [EK].sub.n                                 1e        +     2n                                                                                         ##STR218##                                                                          [E].sub.n                                  1e        +     2o                                                                                         ##STR219##                                                                          [EF].sub.n                                 1e        +     2p                                                                                         ##STR220##                                                                          [EG].sub.n                                 1e        +     2q                                                                                         ##STR221##                                                                          [EH].sub.n                                 1e        +     2w                                                                                         ##STR222##                                                                          [EIFI].sub.n                               1e        +     2x                                                                                         ##STR223##                                                                          [EIGI].sub.n                               1e        +     2y                                                                                         ##STR224##                                                                          [EIHI].sub.n                               1f        +     2a                                                                                         ##STR225##                                                                          [FI].sub.n                                 1f        +     2e                                                                                         ##STR226##                                                                          [FJ].sub.n                                 1f        +     2i                                                                                         ##STR227##                                                                          [FK].sub.n                                 1f        +     2o                                                                                         ##STR228##                                                                          [F].sub.n                                  1f        +     2p                                                                                         ##STR229##                                                                          [FG].sub.n                                 1f        +     2q                                                                                         ##STR230##                                                                          [FH].sub. n                                1f        +     2x                                                                                         ##STR231##                                                                          [FIGI].sub.n                               1f        +     2y                                                                                         ##STR232##                                                                          [FIHI].sub.n                               1g        +     2g                                                                                         ##STR233##                                                                          [GI].sub.n                                 1g        +     2e                                                                                         ##STR234##                                                                          [GJ].sub.n                                 1g        +     2i                                                                                         ##STR235##                                                                          [GK].sub.n                                 1g        +     2p                                                                                         ##STR236##                                                                          [G].sub.n                                  1g        +     2q                                                                                         ##STR237##                                                                          [GH].sub.n                                 1g        +     2y                                                                                         ##STR238##                                                                          [GIHI].sub.n                               1h        +     2a                                                                                         ##STR239##                                                                          [HI].sub.n                                 1h        +     2e                                                                                         ##STR240##                                                                          [HJ].sub.n                                 1h        +     2i                                                                                         ##STR241##                                                                          [HK].sub.n                                 1h        +     2q                                                                                         ##STR242##                                                                          [H].sub.n                                  ______________________________________                                    

                  TABLE 16b                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR243##                                                                    ##STR244##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR245##                                                                           Polymer I(1)                              ______________________________________                                        1a        +     2c                                                                                         ##STR246##                                                                          [AI].sub.n                                 1a        +     2d                                                                                         ##STR247##                                                                          [AI].sub.n                                 1a        +     2g                                                                                         ##STR248##                                                                          [AJ].sub.n                                 1a        +     2h                                                                                         ##STR249##                                                                          [AJ].sub.n                                 1a        +     2r                                                                                         ##STR250##                                                                          [AI].sub.n                                 1a        +     2z                                                                                         ##STR251##                                                                          [A].sub.n                                  1b        +     2b                                                                                         ##STR252##                                                                          [BI].sub.n                                 1b        +     2c                                                                                         ##STR253##                                                                          [BI].sub.n                                 1b        +     2d                                                                                         ##STR254##                                                                          [BI].sub.n                                 1b        +     2f                                                                                         ##STR255##                                                                          [BJ].sub.n                                 1b        +     2g                                                                                         ##STR256##                                                                          [BJ].sub.n                                 1b        +     2h                                                                                         ##STR257##                                                                          [BJ].sub.n                                 1b        +     2r                                                                                         ##STR258##                                                                          [AIBI].sub.n                               1b        +     2s                                                                                         ##STR259##                                                                          [BI].sub.n                                 1b        +     2z                                                                                         ##STR260##                                                                          [B].sub.n                                  1c        +     2b                                                                                         ##STR261##                                                                          [CI].sub.n                                 1c        +     2c                                                                                         ##STR262##                                                                          [CI].sub.n                                 1c        +     2d                                                                                         ##STR263##                                                                          [CI].sub.n                                 1c        +     2f                                                                                         ##STR264##                                                                          [CJ].sub.n                                 1c        +     2g                                                                                         ##STR265##                                                                          [CJ].sub.n                                 1c        +     2h                                                                                         ##STR266##                                                                          [CJ].sub.n                                 1c        +     2r                                                                                         ##STR267##                                                                          [AICI].sub.n                               1c        +     2s                                                                                         ##STR268##                                                                          [BICI].sub.n                               1c        +     2t                                                                                         ##STR269##                                                                          [CI].sub.n                                 1d        +     2b                                                                                         ##STR270##                                                                          [DI].sub.n                                 1d        +     2c                                                                                         ##STR271##                                                                          [DI].sub.n                                 1d        +     2d                                                                                         ##STR272##                                                                          [DI] .sub.n                                1d        +     2f                                                                                         ##STR273##                                                                          [DJ].sub.n                                 1d        +     2g                                                                                         ##STR274##                                                                          [DJ].sub.n                                 1d        +     2h                                                                                         ##STR275##                                                                          [DJ].sub.n                                 1d        +     2j                                                                                         ##STR276##                                                                          [AD].sub.n                                 1d        +     2k                                                                                         ##STR277##                                                                          [BD].sub.n                                 1d        +     2l                                                                                         ##STR278##                                                                          [CD].sub.n                                 1d        +     2r                                                                                         ##STR279##                                                                          [AIDI].sub.n                               1d        +     2s                                                                                         ##STR280##                                                                          [BIDI].sub.n                               1d        +     2t                                                                                         ##STR281##                                                                          [CIDI].sub.n                               1d        +     2u                                                                                         ##STR282##                                                                          [DI].sub.n                                 1e        +     2b                                                                                         ##STR283##                                                                          [EI].sub.n                                 1e        +     2c                                                                                         ##STR284##                                                                          [EI].sub.n                                 1e        +     2d                                                                                         ##STR285##                                                                          [EI].sub.n                                 1e        +     2f                                                                                         ##STR286##                                                                          [EJ].sub.n                                 1e        +     2g                                                                                         ##STR287##                                                                          [EJ].sub.n                                 1e        +     2h                                                                                         ##STR288##                                                                          [EJ].sub.n                                 1e        +     2j                                                                                         ##STR289##                                                                          [AE].sub.n                                 1e        +     2k                                                                                         ##STR290##                                                                          [BE].sub.n                                 1e        +     2l                                                                                         ##STR291##                                                                          [CE].sub.n                                 1e        +     2m                                                                                         ##STR292##                                                                          [DE].sub.n                                 1e        +     2r                                                                                         ##STR293##                                                                          [AIEI].sub.n                               1e        +     2s                                                                                         ##STR294##                                                                          [BIEI].sub.n                               1e        +     2t                                                                                         ##STR295##                                                                          [CIEI].sub.n                               1e        +     2u                                                                                         ##STR296##                                                                          [DIEI].sub.n                               1e        +     2v                                                                                         ##STR297##                                                                          [EI].sub.n                                 1f        +     2b                                                                                         ##STR298##                                                                          [FI].sub.n                                 1f        +     2c                                                                                         ##STR299##                                                                          [FI].sub.n                                 1f        +     2d                                                                                         ##STR300##                                                                          [FI].sub.n                                 1f        +     2f                                                                                         ##STR301##                                                                          [FJ].sub.n                                 1f        +     2g                                                                                         ##STR302##                                                                          [FJ].sub.n                                 1f        +     2h                                                                                         ##STR303##                                                                          [FJ].sub.n                                 1f        +     2j                                                                                         ##STR304##                                                                          [AF].sub.n                                 1f        +     2k                                                                                         ##STR305##                                                                          [BF].sub.n                                 1f        +     2l                                                                                         ##STR306##                                                                          [CF].sub.n                                 1f        +     2m                                                                                         ##STR307##                                                                          [DF].sub.n                                 1f        +     2n                                                                                         ##STR308##                                                                          [EF].sub.n                                 1f        +     2r                                                                                         ##STR309##                                                                          [AIFI].sub.n                               1f        +     2s                                                                                         ##STR310##                                                                          [BIFI].sub.n                               1f        +     2t                                                                                         ##STR311##                                                                          [CIFI].sub.n                               1f        +     2u                                                                                         ##STR312##                                                                          [DIFI].sub.n                               1f        +     2v                                                                                         ##STR313##                                                                          [EIFI].sub.n                               1f        +     2w                                                                                         ##STR314##                                                                          [FI].sub.n                                 1g        +     2b                                                                                         ##STR315##                                                                          [GI].sub.n                                 1g        +     2c                                                                                         ##STR316##                                                                          [GI].sub.n                                 1g        +     2d                                                                                         ##STR317##                                                                          [GI].sub.n                                 1g        +     2f                                                                                         ##STR318##                                                                          [GJ].sub.n                                 1g        +     2g                                                                                         ##STR319##                                                                          [GJ].sub. n                                1g        +     2h                                                                                         ##STR320##                                                                          [GJ].sub.n                                 1g        +     2j                                                                                         ##STR321##                                                                          [AG].sub.n                                 1g        +     2k                                                                                         ##STR322##                                                                          [BG].sub.n                                 1g        +     2l                                                                                         ##STR323##                                                                          [CG].sub.n                                 1g        +     2m                                                                                         ##STR324##                                                                          [DG].sub.n                                 1g        +     2n                                                                                         ##STR325##                                                                          [EG].sub.n                                 1g        +     2o                                                                                         ##STR326##                                                                          [FG].sub.n                                 1g        +     2r                                                                                         ##STR327##                                                                          [AIGI].sub.n                               1g        +     2s                                                                                         ##STR328##                                                                          [BIGI].sub.n                               1g        +     2t                                                                                         ##STR329##                                                                          [CIGI].sub.n                               1g        +     2u                                                                                         ##STR330##                                                                          [DIGI].sub.n                               1g        +     2v                                                                                         ##STR331##                                                                          [EIGI].sub.n                               1g        +     2w                                                                                         ##STR332##                                                                          [FIGI[.sub.n                               1g        +     2x                                                                                         ##STR333##                                                                          [GI].sub.n                                 1h        +     2b                                                                                         ##STR334##                                                                          [HI].sub.n                                 1h        +     2c                                                                                         ##STR335##                                                                          [HI].sub.n                                 1h        +     2d                                                                                         ##STR336##                                                                          [HI].sub.n                                 1h        +     2f                                                                                         ##STR337##                                                                          [HJ].sub.n                                 1h        +     2g                                                                                         ##STR338##                                                                          [HJ].sub.n                                 1h        +     2h                                                                                         ##STR339##                                                                          [HJ].sub.n                                 1h        +     2j                                                                                         ##STR340##                                                                          [AH].sub.n                                 1h        +     2k                                                                                         ##STR341##                                                                          [BH].sub.n                                 1h        +     2l                                                                                         ##STR342##                                                                          [CH].sub.n                                 1h        +     2m                                                                                         ##STR343##                                                                          [DH].sub.n                                 1h        +     2n                                                                                         ##STR344##                                                                          [EH].sub.n                                 1h        +     2o                                                                                         ##STR345##                                                                          [FH].sub.n                                 1h        +     2p                                                                                         ##STR346##                                                                          [GH].sub.n                                 1h        +     2r                                                                                         ##STR347##                                                                          [AIHI].sub.n                               1h        +     2s                                                                                         ##STR348##                                                                          [BIHI].sub.n                               1h        +     2t                                                                                         ##STR349##                                                                          [CIHI].sub.n                               1h        +     2u                                                                                         ##STR350##                                                                          [DIHI].sub.n                               1h        +     2v                                                                                         ##STR351##                                                                          [EIHI].sub.n                               1h        +     2w                                                                                         ##STR352##                                                                          [FIHI].sub.n                               1h        +     2x                                                                                         ##STR353##                                                                          [GIHI].sub.n                               1h        +     2y                                                                                         ##STR354##                                                                          [HI].sub.n                                 ______________________________________                                    

                  TABLE 17a                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR355##                                                                    ##STR356##                                                                    Monomer (1,2)                                                                           +     Monomer (2,1)                                                                             ##STR357##                                                                           Polymer I(2)                              ______________________________________                                        1i        +     2b                                                                                         ##STR358##                                                                          [LI].sub.n                                 1i        +     2c                                                                                         ##STR359##                                                                          [LI].sub.n                                 1i        +     2d                                                                                         ##STR360##                                                                          [LI].sub.n                                 1i        +     2e                                                                                         ##STR361##                                                                          [LJ].sub.n                                 1i        +     2f                                                                                         ##STR362##                                                                          [LJ].sub.n                                 1i        +     2g                                                                                         ##STR363##                                                                          [LJ].sub.n                                 1i        +     2h                                                                                         ##STR364##                                                                          [LJ].sub.n                                 1i        +     2i                                                                                         ##STR365##                                                                          [LK].sub.n                                 1i        +     2k                                                                                         ##STR366##                                                                          [BL].sub.n                                 1i        +     2l                                                                                         ##STR367##                                                                          [CL].sub.n                                 1i        +     2m                                                                                         ##STR368##                                                                          [DL].sub.n                                 1i        +     2n                                                                                         ##STR369##                                                                          [EL].sub.n                                 1i        +     2o                                                                                         ##STR370##                                                                          [FL].sub.n                                 1i        +     2p                                                                                         ##STR371##                                                                          [GL].sub.n                                 1i        +     2q                                                                                         ##STR372##                                                                          [HL].sub.n                                 1i        +     2r                                                                                         ##STR373##                                                                          [AILI].sub.n                               1i        +     2s                                                                                         ##STR374##                                                                          [BILI].sub.n                               1i        +     2t                                                                                         ##STR375##                                                                          [CILI].sub.n                               1i        +     2u                                                                                         ##STR376##                                                                          [DILI].sub.n                               1i        +     2v                                                                                         ##STR377##                                                                          [EILI].sub.n                               1i        +     2w                                                                                         ##STR378##                                                                          [FILI].sub.n                               1i        +     2x                                                                                         ##STR379##                                                                          [GILI].sub.n                               1i        +     2y                                                                                         ##STR380##                                                                          [HILI].sub.n                               1i        +     2z                                                                                         ##STR381##                                                                          [L].sub.n                                  1j        +     2b                                                                                         ##STR382##                                                                          [MI].sub.n                                 1j        +     2c                                                                                         ##STR383##                                                                          [MI].sub.n                                 1j        +     2d                                                                                         ##STR384##                                                                          [MI] .sub.n                                1j        +     2e                                                                                         ##STR385##                                                                          [MJ].sub.n                                 1j        +     2f                                                                                         ##STR386##                                                                          [MJ].sub.n                                 1j        +     2g                                                                                         ##STR387##                                                                          [MJ].sub.n                                 1j        +     2h                                                                                         ##STR388##                                                                          [MJ].sub.n                                 1j        +     2i                                                                                         ##STR389##                                                                          [MK].sub.n                                 1j        +     2k                                                                                         ##STR390##                                                                          [BM].sub.n                                 1j        +     2l                                                                                         ##STR391##                                                                          [CM].sub.n                                 1j        +     2m                                                                                         ##STR392##                                                                          [DM].sub.n                                 1j        +     2n                                                                                         ##STR393##                                                                          [EM].sub.n                                 1j        +     2o                                                                                         ##STR394##                                                                          [FM].sub.n                                 1j        +     2p                                                                                         ##STR395##                                                                          [GM].sub.n                                 1j        +     2q                                                                                         ##STR396##                                                                          [HM].sub.n                                 1j        +     2r                                                                                         ##STR397##                                                                          [AIMI].sub.n                               1j        +     2s                                                                                         ##STR398##                                                                          [BIMI].sub.n                               1j        +     2t                                                                                         ##STR399##                                                                          [CIMI].sub.n                               1j        +     2u                                                                                         ##STR400##                                                                          [DIMI].sub.n                               1j        +     2v                                                                                         ##STR401##                                                                          [EIMI].sub.n                               1j        +     2w                                                                                         ##STR402##                                                                          [FIMI].sub.n                               1j        +     2x                                                                                         ##STR403##                                                                          [GIMI].sub.n                               1j        +     2y                                                                                         ##STR404##                                                                          [HIMI].sub.n                               1j        +     2z                                                                                         ##STR405##                                                                          [M].sub.n                                  1k        +     2b                                                                                         ##STR406##                                                                          [NI].sub.n                                 1k        +     2c                                                                                         ##STR407##                                                                          [NI].sub.n                                 1k        +     2d                                                                                         ##STR408##                                                                          [NI].sub.n                                 1k        +     2e                                                                                         ##STR409##                                                                          [NJ].sub.n                                 1k        +     2f                                                                                         ##STR410##                                                                          [NJ].sub.n                                 1k        +     2g                                                                                         ##STR411##                                                                          [NJ].sub.n                                 1k        +     2h                                                                                         ##STR412##                                                                          [NJ].sub.n                                 1k        +     2i                                                                                         ##STR413##                                                                          [NK].sub.n                                 1k        +     2k                                                                                         ##STR414##                                                                          [BN].sub.n                                 1k        +     2l                                                                                         ##STR415##                                                                          [CN].sub.n                                 1k        +     2m                                                                                         ##STR416##                                                                          [DN].sub.n                                 1k        +     2n                                                                                         ##STR417##                                                                          [EN].sub.n                                 1k        +     2o                                                                                         ##STR418##                                                                          [FN].sub.n                                 1k        +     2p                                                                                         ##STR419##                                                                          [GN].sub.n                                 1k        +     2q                                                                                         ##STR420##                                                                          [HN].sub.n                                 1k        +     2r                                                                                         ##STR421##                                                                          [AINI].sub.n                               1k        +     2s                                                                                         ##STR422##                                                                          [BINI].sub.n                               1k        +     2t                                                                                         ##STR423##                                                                          [CINI].sub.n                               1k        +     2u                                                                                         ##STR424##                                                                          [DINI].sub.n                               1k        +     2v                                                                                         ##STR425##                                                                          [EINI].sub.n                               1k        +     2w                                                                                         ##STR426##                                                                          [FINI].sub.n                               1k        +     2x                                                                                         ##STR427##                                                                          [GINI].sub.n                               1k        +     2y                                                                                         ##STR428##                                                                          [HINI].sub.n                               1k        +     2z                                                                                         ##STR429##                                                                          [N].sub.n                                  1l        +     2b                                                                                         ##STR430##                                                                          [OI].sub.n                                 1l        +     2c                                                                                         ##STR431##                                                                          [OI].sub. n                                1l        +     2d                                                                                         ##STR432##                                                                          [OI].sub.n                                 1l        +     2e                                                                                         ##STR433##                                                                          [OJ].sub.n                                 1l        +     2f                                                                                         ##STR434##                                                                          [OJ].sub.n                                 1l        +     2g                                                                                         ##STR435##                                                                          [OJ].sub.n                                 1l        +     2h                                                                                         ##STR436##                                                                          [OJ].sub.n                                 1l        +     2i                                                                                         ##STR437##                                                                          [OK].sub.n                                 1l        +     2j                                                                                         ##STR438##                                                                          [AO].sub.n                                 1l        +     2k                                                                                         ##STR439##                                                                          [BO].sub.n                                 1l        +     2l                                                                                         ##STR440##                                                                          [CO].sub.n                                 1l        +     2m                                                                                         ##STR441##                                                                          [DO].sub.n                                 1l        +     2n                                                                                         ##STR442##                                                                          [EO].sub.n                                 1l        +     2o                                                                                         ##STR443##                                                                          [FO].sub.n                                 1l        +     2p                                                                                         ##STR444##                                                                          [GO].sub.n                                 1l        +     2q                                                                                         ##STR445##                                                                          [HO].sub.n                                 1l        +     2r                                                                                         ##STR446##                                                                          [AIOI].sub.n                               1l        +     2s                                                                                         ##STR447##                                                                          [BIOI].sub.n                               1l        +     2t                                                                                         ##STR448##                                                                          [CIOI].sub.n                               1l        +     2u                                                                                         ##STR449##                                                                          [DIOI].sub.n                               1l        +     2v                                                                                         ##STR450##                                                                          [EIOI].sub.n                               1l        +     2w                                                                                         ##STR451##                                                                          [FIOI].sub.n                               1l        +     2x                                                                                         ##STR452##                                                                          [GIOI].sub.n                               1l        +     2y                                                                                         ##STR453##                                                                          [HIOI].sub.n                               1m        +     2a                                                                                         ##STR454##                                                                          [PI].sub.n                                 1m        +     2b                                                                                         ##STR455##                                                                          [PI].sub.n                                 1m        +     2c                                                                                         ##STR456##                                                                          [PI].sub.n                                 1m        +     2d                                                                                         ##STR457##                                                                          [PI].sub.n                                 1m        +     2e                                                                                         ##STR458##                                                                          [PJ].sub.n                                 1m        +     2f                                                                                         ##STR459##                                                                          [PJ].sub.n                                 1m        +     2g                                                                                         ##STR460##                                                                          [PJ].sub.n                                 1m        +     2h                                                                                         ##STR461##                                                                          [PJ].sub.n                                 1m        +     2i                                                                                         ##STR462##                                                                          [PK].sub.n                                 1m        +     2j                                                                                         ##STR463##                                                                          [AP].sub.n                                 1m        +     2k                                                                                         ##STR464##                                                                          [BP].sub.n                                 1m        +     2l                                                                                         ##STR465##                                                                          [CP].sub.n                                 1m        +     2m                                                                                         ##STR466##                                                                          [DP].sub.n                                 1m        +     2n                                                                                         ##STR467##                                                                          [EP].sub.n                                 1m        +     2o                                                                                         ##STR468##                                                                          [FP].sub.n                                 1m        +     2p                                                                                         ##STR469##                                                                          [GP].sub.n                                 1m        +     2q                                                                                         ##STR470##                                                                          [HP].sub.n                                 1m        +     2r                                                                                         ##STR471##                                                                          [AIPI].sub.n                               1m        +     2s                                                                                         ##STR472##                                                                          [BIPI].sub.n                               1m        +     2t                                                                                         ##STR473##                                                                          [CIPI].sub.n                               1m        +     2u                                                                                         ##STR474##                                                                          [DIPI].sub.n                               1m        +     2v                                                                                         ##STR475##                                                                          [EIPI].sub.n                               1m        +     2w                                                                                         ##STR476##                                                                          [FIPI].sub.n                               1m        +     2x                                                                                         ##STR477##                                                                          [GIPI].sub.n                               1m        +     2y                                                                                         ##STR478##                                                                          [HIPI].sub.n                               1n        +     2a                                                                                         ##STR479##                                                                          [QI].sub.n                                 1n        +     2b                                                                                         ##STR480##                                                                          [QI].sub.n                                 1n        +     2c                                                                                         ##STR481##                                                                          [QI].sub.n                                 1n        +     2d                                                                                         ##STR482##                                                                          [QI].sub.n                                 1n        +     2e                                                                                         ##STR483##                                                                          [QJ].sub.n                                 1n        +     2f                                                                                         ##STR484##                                                                          [QJ].sub.n                                 1n        +     2g                                                                                         ##STR485##                                                                          [QJ].sub.n                                 1n        +     2h                                                                                         ##STR486##                                                                          [QJ].sub.n                                 1n        +     2i                                                                                         ##STR487##                                                                          [QK].sub.n                                 1n        +     2j                                                                                         ##STR488##                                                                          [AQ].sub.n                                 1n        +     2k                                                                                         ##STR489##                                                                          [BQ].sub.n                                 1n        +     2l                                                                                         ##STR490##                                                                           [CQ].sub.n                                1n        +     2m                                                                                         ##STR491##                                                                          [DQ].sub.n                                 1n        +     2n                                                                                         ##STR492##                                                                          [EQ].sub.n                                 1n        +     2o                                                                                         ##STR493##                                                                          [FQ].sub.n                                 1n        +     2p                                                                                         ##STR494##                                                                          [GQ].sub.n                                 1n        +     2q                                                                                         ##STR495##                                                                          [HQ].sub.n                                 1n        +     2r                                                                                         ##STR496##                                                                          [AIQI].sub.n                               1n        +     2s                                                                                         ##STR497##                                                                          [BIQI].sub.n                               1n        +     2t                                                                                         ##STR498##                                                                          [CIQI].sub.n                               1n        +     2u                                                                                         ##STR499##                                                                          [DIQI].sub.n                               1n        +     2v                                                                                         ##STR500##                                                                          [EIQI].sub.n                               1n        +     2w                                                                                         ##STR501##                                                                          [FIQI].sub.n                               1n        +     2x                                                                                         ##STR502##                                                                          [GIQI].sub.n                               1n        +     2y                                                                                         ##STR503##                                                                          [HIQI].sub.n                               1n        +     2z                                                                                         ##STR504##                                                                          [Q].sub.n                                  1o        +     2a                                                                                         ##STR505##                                                                          [RI].sub.n                                 1o        +     2b                                                                                         ##STR506##                                                                          [RI].sub.n                                 1o        +     2c                                                                                         ##STR507##                                                                          [RI].sub.n                                 1o        +     2d                                                                                         ##STR508##                                                                          [RI].sub.n                                 1o        +     2e                                                                                         ##STR509##                                                                          [RJ].sub.n                                 1o        +     2f                                                                                         ##STR510##                                                                          [RJ].sub.n                                 1o        +     2g                                                                                         ##STR511##                                                                          [RJ].sub.n                                 1o        +     2h                                                                                         ##STR512##                                                                          [RJ].sub.n                                 1o        +     2i                                                                                         ##STR513##                                                                          [RK].sub.n                                 1o        +     2j                                                                                         ##STR514##                                                                          [AR].sub.n                                 1o        +     2k                                                                                         ##STR515##                                                                          [BR].sub.n                                 1o        +     2l                                                                                         ##STR516##                                                                          [CR].sub.n                                 1o        +     2m                                                                                         ##STR517##                                                                          [DR].sub.n                                 1o        +     2n                                                                                         ##STR518##                                                                          [ER].sub.n                                 1o        +     2o                                                                                         ##STR519##                                                                          [FR].sub.n                                 1o        +     2p                                                                                         ##STR520##                                                                          [GR].sub.n                                 1o        +     2q                                                                                         ##STR521##                                                                          [HR].sub.n                                 1o        +     2r                                                                                         ##STR522##                                                                          [AIRI].sub.n                               1o        +     2s                                                                                         ##STR523##                                                                          [BIRI].sub.n                               1o        +     2t                                                                                         ##STR524##                                                                          [CIRI].sub.n                               1o        +     2u                                                                                         ##STR525##                                                                          [DIRI].sub.n                               1o        +     2v                                                                                         ##STR526##                                                                          [EIRI].sub.n                               1o        +     2w                                                                                         ##STR527##                                                                          [FIRI].sub.n                               1o        +     2x                                                                                         ##STR528##                                                                          [GIRI].sub.n                               1o        +     2y                                                                                         ##STR529##                                                                          [HIRI].sub.n                               1o        +     2z                                                                                         ##STR530##                                                                          [R].sub.n                                  1p        +     2a                                                                                         ##STR531##                                                                          [SI].sub.n                                 1p        +     2b                                                                                         ##STR532##                                                                          [SI].sub.n                                 1p        +     2c                                                                                         ##STR533##                                                                          [SI].sub.n                                 1p        +     2d                                                                                         ##STR534##                                                                          [SI].sub.n                                 1p        +     2e                                                                                         ##STR535##                                                                          [SJ].sub.n                                 1p        +     2f                                                                                         ##STR536##                                                                          [SJ].sub.n                                 1p        +     2g                                                                                         ##STR537##                                                                          [SJ] .sub.n                                1p        +     2h                                                                                         ##STR538##                                                                          [SJ].sub.n                                 1p        +     2i                                                                                         ##STR539##                                                                          [SK].sub.n                                 1p        +     2j                                                                                         ##STR540##                                                                          [AS].sub.n                                 1p        +     2k                                                                                         ##STR541##                                                                          [BS].sub.n                                 1p        +     2l                                                                                         ##STR542##                                                                          [CS].sub.n                                 1p        +     2m                                                                                         ##STR543##                                                                          [DS].sub.n                                 1p        +     2n                                                                                         ##STR544##                                                                          [ES].sub.n                                 1p        +     2o                                                                                         ##STR545##                                                                          [FS].sub.n                                 1p        +     2p                                                                                         ##STR546##                                                                          [GS].sub.n                                 1p        +     2q                                                                                         ##STR547##                                                                          [HS].sub.n                                 1p        +     2r                                                                                         ##STR548##                                                                          [AISI].sub.n                               1p        +     2s                                                                                         ##STR549##                                                                          [BISI].sub.n                               1p        +     2t                                                                                         ##STR550##                                                                          [CISI].sub.n                               1p        +     2u                                                                                         ##STR551##                                                                          [DISI].sub.n                               1p        +     2v                                                                                         ##STR552##                                                                          [EISI].sub.n                               1p        +     2w                                                                                         ##STR553##                                                                          [FISI].sub.n                               1p        +     2x                                                                                         ##STR554##                                                                          [GISI].sub.n                               1p        +     2y                                                                                         ##STR555##                                                                          [HISI].sub.n                               ______________________________________                                    

                  TABLE 17b                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR556##                                                                    ##STR557##                                                                    Monomer (1,1) + Monomer (2,2)                                                                    ##STR558##                                                                             Polymer I(2)                                     ______________________________________                                         1a + 2hh                                                                                         ##STR559##                                                                             [AVIV'] .sub.n                                    1a + 2ii                                                                                         ##STR560##                                                                             [ATIT'] .sub.n                                    1a + 2jj                                                                                         ##STR561##                                                                             [ATKT'] .sub.n                                    1b + 2hh                                                                                         ##STR562##                                                                             [BVIV'] .sub.n                                    1b + 2ii                                                                                         ##STR563##                                                                             [BTIT'] .sub.n                                    1b + 2jj                                                                                         ##STR564##                                                                             [BTKT'] .sub.n                                    1c + 2hh                                                                                         ##STR565##                                                                             [CVIV'] .sub.n                                    1c + 2ii                                                                                         ##STR566##                                                                             [CTIT'] .sub.n                                    1c + 2jj                                                                                         ##STR567##                                                                             [CTKT'] .sub.n                                    1d + 2hh                                                                                         ##STR568##                                                                             [DVIV' ] .sub.n                                   1d + 2ii                                                                                         ##STR569##                                                                             [DTIT'] .sub.n                                    1d + 2jj                                                                                         ##STR570##                                                                             [DTKT'] .sub.n                                    1e + 2hh                                                                                         ##STR571##                                                                             [EVIV'] .sub.n                                    1e + 2hh                                                                                         ##STR572##                                                                             [ETIT'] .sub.n                                    1e + 2jj                                                                                         ##STR573##                                                                             [ETKT'] .sub.n                                    1f + 2hh                                                                                         ##STR574##                                                                             [FVIV'] .sub.n                                    1f + 2ii                                                                                         ##STR575##                                                                             [FTIT'] .sub.n                                    1f +  2jj                                                                                        ##STR576##                                                                             [FTKT'] .sub.n                                    1g + 2hh                                                                                         ##STR577##                                                                             [GVIV'] .sub.n                                    1g + 2ii                                                                                         ##STR578##                                                                             [GTIT'] .sub.n                                    1g + 2jj                                                                                         ##STR579##                                                                             [GTKT'] .sub.n                                    1h + 2hh                                                                                         ##STR580##                                                                             [HVIV'] .sub.n                                    1h + 2ii                                                                                         ##STR581##                                                                             [HTIT'] .sub.n                                    1h + 2jj                                                                                         ##STR582##                                                                             [HTKT'] .sub.n                                   ______________________________________                                    

                  TABLE 17c                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR583##                                                                    ##STR584##                                                                    Monomer (1,2) + Monomer (2,2)                                                                    ##STR585##                                                                             Polymer I(2)                                     ______________________________________                                         1i + 2hh                                                                                         ##STR586##                                                                             [LVIV'] .sub.n                                    1i + 2ii                                                                                         ##STR587##                                                                             [LTIT'] .sub.n                                    1i + 2jj                                                                                         ##STR588##                                                                             [LTKT'] .sub.n                                    1j + 2hh                                                                                         ##STR589##                                                                             [MVIV'] .sub.n                                    1j + 2ii                                                                                         ##STR590##                                                                             [MTIT'] .sub.n                                    1j + 2jj                                                                                         ##STR591##                                                                             [MTKT'] .sub.n                                    1k + 2hh                                                                                         ##STR592##                                                                             [NVIV'] .sub.n                                    1k + 2ii                                                                                         ##STR593##                                                                             [NTIT'] .sub.n                                    1k + 2jj                                                                                         ##STR594##                                                                             [NTKT'] .sub.n                                    1l + 2hh                                                                                         ##STR595##                                                                             [OVIV' ] .sub.n                                   1l + 2ii                                                                                         ##STR596##                                                                             [OTIT'] .sub.n                                    1l + 2jj                                                                                         ##STR597##                                                                             [OTKT'] .sub.n                                    1m + 2hh                                                                                         ##STR598##                                                                             [PVIV'] .sub.n                                    1m + 2ii                                                                                         ##STR599##                                                                             [PTIT'] .sub.n                                    1m + 2jj                                                                                         ##STR600##                                                                             [PTKT'] .sub.n                                    1n + 2hh                                                                                         ##STR601##                                                                             [QVIV'] .sub.n                                    1n + 2ii                                                                                         ##STR602##                                                                             [QTIT'] .sub.n                                    1n +  2jj                                                                                        ##STR603##                                                                             [QTKT'] .sub.n                                    1o + 2hh                                                                                         ##STR604##                                                                             [RVIV'] .sub.n                                    1o + 2ii                                                                                         ##STR605##                                                                             [RTIT'] .sub.n                                    1o + 2jj                                                                                         ##STR606##                                                                             [RTKT'] .sub.n                                    1p + 2hh                                                                                         ##STR607##                                                                             [SVIV'] .sub.n                                    1p + 2ii                                                                                         ##STR608##                                                                             [STIT'] .sub.n                                    1p + 2jj                                                                                         ##STR609##                                                                             [STKT'] .sub.n                                   ______________________________________                                    

EXAMPLE 26

A solution consisting of 63.34 g concentrated phosphoric acid and 147.59g of 115% PPA was stirred at 100° C. under reduced pressure for 3h in a300 ml 3-necked flask. To a 500 mL resin kettle was added 63.49 g(0.3087 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a)(prepared by the method of Wolfe, AFOSR Final Technical Report, Dec. 15,1980). A portion of the above-prepared PPA having a P₂ O₅ of 77.3%(207.57 g) was poured into the resin kettle containing the monomer whileunder argon flow. After the monomer had been incorporated, a secondportion of monomer (30.71 g, 0.1493 mol) was added. The mixture washeated to 55° C. and the pressure was gradually decreased over 1.5h. Anadditional 5.35 g of monomer was added to the kettle under argon flowbringing the total monomer added to 99.65 g (0.4845 mol). The mixturewas then stirred under reduced pressure at 50° C. overnight. Thetemperature was then raised to 70° C. for 8h. Phosphorus pentoxide(138.62 g) was then added in one portion to increase the effective P₂ O₅content to 86.4%. After heating at 100° C. with stirring overnight thereaction product was stir-opalescent. After placing the mixture, whichstill contained undissolved monomer, under reduced pressure for 3h, asample was removed and was placed between a microscope slide and a coverglass. The unprecipitated product depolarized plane-polarized light. Thereaction mixture was then heated under argon as follows: an additional2.5h at 100° C.; 2h at 120° C.; 16h at 130° C.; 31h at 170° C.; 43.5h at200° C. A sample of the green, opalescent polymer reaction productyielded gold-orange fibers upon precipitation in water. The sample wasextracted in water for 24h and dried under vacuum at 140° C. for 24h.The intrinsic viscosity was determined to be 8.2 dL/g in MSA at 30.1° C.The reaction product is characterized as having a final effective P₂ O₅content of 82.2% with the polymer --I]_(n) having a concentration of15.1% by weight.

EXAMPLE 27

A mixture of 125.8 g of 115% PPA and 53.9 g of concentrated phosphoricacid (85.7% H₃ PO₄) was heated to 100° C. for 4h under reduced pressurein a 500 mL 3-necked flask. To a 500 mL resin kettle was added 91.85 g(0.4466 mol) of 3a. The kettle containing the monomer was deaerated.108.17 g of the PPA prepared above (having a P₂ O₅ content of 77.2%) wasthen added. The kettle was then heated with an oil bath at 50° C. undera thin stream of argon overnight. The kettle was then placed underreduced pressure again and heated to 70° C. for 23h. P₂ O₅ (108.32 g)was then added in three portions to increase the effective P₂ O₅ contentto 88.5%. Reduced pressure was applied to degas the P₂ O₅ and to causefoaming that aided in mixing. After 3h of stirring the temperature wasraised to 100° C. and maintained at that temperture under reducedpressure for 21h. The mixture was stir-opalescent and depolarizedplane-polarized light. The mixture was then heated as follows: 115° C.under argon for 3h; 130° C. under reduced pressure for 2h; 170° C. for0.5h; 190° C. for 17h. A sample of the green, opalescent reactionproduct was removed and gave a fibrillar, golden-colored fiber upondrawing followed by precipitation in water. After extracting with waterin a Soxhlet apparatus for 24h the sample was dried for 24h at 110° C.under reduced pressure. The intrinsic viscosity of this sample was 15.8dL/g in MSA at 30° C. An additional 7.5h of heating gave a sample withan intrinsic viscosity of 16.7 dL/g. The reaction product thus obtainedwas 20.3% by weight of polymer --T]_(n) in PPA with a final P₂ O₅content of 82.4%.

EXAMPLE 28

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 146.9123 g (0.4305753 mol) of monomer 3k is dehydrochlorinated in an"initial" solution of 265.9 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 78.6 g of 85.4% H₃ PO₄ with 187.4 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 144.85g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to the schedule given in Example 27.The amount of P₂ O₅ added is preselected (as determined in accord withthe aforementioned formulae a* and b*) to provide the reaction mixturewith an effective P₂ O₅ content of approximately 85.3% prior to thestart of polymerization and an effective P₂ O₅ content of approximately82.2% subsequent to substantial complete polymerization. The reactionproduct obtained exhibits stir-opalescence and is further characterizedas having a polymer concentration of 19%; fibers are readily formed bydirect spinning, or drawing from the reaction product. The polymerobtained is of the following structure:

    --CI].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.which corresponds to an average n value of polymerization of about 70.

EXAMPLE 29

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3c is dehydrochlorinated in an"initial" solution of 198.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 58.7 g of 85.4% H₃ PO₄ with 140.0 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 196.8g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.6% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --U].sub.n

characterized by an intrinsic viscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 30

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3d is dehydrochlorinated in an"initial" solution of 221.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 65.50 g of 85.4% H₃ PO₄ with 156.2 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 203.1g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.2% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 18%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: characterized by an intrinsic viscosity of12 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 26-30, other Type II extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 19. The e→denotes especially preferred selected monomer reactions.

                  TABLE 19                                                        ______________________________________                                        Polymers of Type II, Class 2                                                  Polymerization Reactions:                                                      ##STR610##                                                                    Monomer (3,2)                                                                                ##STR611##                                                                             Polymer II(2)                                        ______________________________________                                         3f                                                                                           ##STR612##                                                                             [X] .sub.n                                            3g                                                                                           ##STR613##                                                                             [Y] .sub.n                                            3h                                                                                           ##STR614##                                                                             [TI] .sub.n                                           3i                                                                                           ##STR615##                                                                             [UI] .sub.n                                          ______________________________________                                    

EXAMPLE 31

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 99.923 g (0.35182 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 602.0 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 177.9 g of 85.4% H₃ PO₄ with 424.1 g of 115% PPA).When dehydrochlorination is substantially complete, 76.740 g (0.35182mol) of monomer 4a is added followed by the gradual addition of 272.7 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 84.4%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 10%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --ZB'A'B'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 31, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 20. The e→denotes especially preferred selected monomer reactions.

                  TABLE 20                                                        ______________________________________                                        Polymers of Type III, Class 1                                                 Polymerization Reactions:                                                      ##STR616##                                                                    ##STR617##                                                                    Monomer (1,1) + Monomer (4,1)                                                                    ##STR618##                                                                             Polymer III(1)                                   ______________________________________                                         1c + 4b                                                                                          ##STR619##                                                                             [B'A'F'Z] .sub.n                                   1e + 4a                                                                                         ##STR620##                                                                             [C'A'B'Z] .sub.n                                  1e + 4b                                                                                          ##STR621##                                                                             [C'A'F'Z] .sub.n                                 ______________________________________                                    

EXAMPLE 32

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 109.94 g (0.27752 mol) of monomer 11 is dehydrochlorinated inan "initial" solution of 317.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 93.7 g of 85.4% H₃ PO₄ with 223.5 g of 115% PPA).When dehydrochlorination is substantially complete, 60.533 g (0.27752mol) of monomer 4a is added followed by the gradual addition of 219.5 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --ZD'A'B'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.Analogous to the foregoing Example 32, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reactions in Table 21. The e→denotes especially preferred selected monomer reactions.

                  TABLE 21                                                        ______________________________________                                        Polymers of Type III, Class 2                                                 Polymerization Reactions:                                                      ##STR622##                                                                    ##STR623##                                                                    Monomer (1,2) + Monomer (4,1)                                                                    ##STR624##                                                                             Polymer III(2)                                   ______________________________________                                         1l + 4a                                                                                          ##STR625##                                                                             [D'A'B'Z] .sub.n                                   1l + 4b                                                                                         ##STR626##                                                                             [D'A'F'Z] .sub.n                                  1p + 4a                                                                                          ##STR627##                                                                             [E'A'B'Z] .sub.n                                  1p + 4b                                                                                          ##STR628##                                                                             [E'A'F'Z] .sub.n                                 ______________________________________                                    

EXAMPLE 33

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 117.5156 g (0.5149463 mol) of monomer 5a is dissolved in an"initial" solution of 623.7 g of PPA having a P₂ O₅ content of 77.0%(prepared by mixing 192.8 g of 85.4% H₃ PO₄ with 430.9 g of 115% PPA).When dissolution is substantially complete, an additional 257.8 g of P₂O₅ is gradually added to the mixture and dissolved by stirring andheating essentially according to Example 27. The amount of P₂ O₅ addedis preselected (as determined in accord with the aforementioned formulaea* and b*) to provide the reaction mixture with an effective P₂ O₅content of approximately 83.7% prior to the start of polymerization andan effective P₂ O₅ content of approximately 82.0% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 10%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --F'A'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 34

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.784 g (0.28869 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 242.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 71.7 g of 85.4% H₃ O₄ with 171.0 g of 115% PPA).When dehydrochlorination is substantially complete, 71.070 g (0.28869mol) of monomer 6a is added followed by the gradual addition of 162.9 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.4% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'G'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 35

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 67.798 g (0.31820 mol) of monomer 1b is dehydrochlorinated inan "initial" mixture of 343.3 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 101.4 g of 85.4% H₃ PO₄ with 241.9 g of 115% PPA).When dehydrochlorination is substantially complete, 78.336 g (0.31820mol) of monomer 6a is added followed by the gradual addition of 200.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formula a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'H'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 36

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 90.945 g (0.32021 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 402.5 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 192.1 g of 85.4% H₃ PO₄ with 210.4 g of 115% PPA).When dehydrochlorination is substantially complete, 78.830 g (0.32021mol) of monomer 6a is added followed by the gradual addition of 307.8 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.9% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'I'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 34-36, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 23. The e→denotes especially preferred selected monomer reactions.

                  TABLE 23                                                        ______________________________________                                        Polymers of Type V, Class 1                                                   Polymerization Reactions:                                                      ##STR629##                                                                    ##STR630##                                                                    Monomer (1,1) + Monomer (6,1)                                                                    ##STR631##                                                                             Polymer V(1)                                     ______________________________________                                         1d + 6a                                                                                          ##STR632##                                                                             [B'H'] .sub.n*                                    1e + 6a                                                                                          ##STR633##                                                                             [C'I'] .sub.n                                     1f + 6a                                                                                          ##STR634##                                                                             [C'H'] .sub.n                                     1g + 6a                                                                                          ##STR635##                                                                             [C'G'] .sub.n                                     1h + 6a                                                                                          ##STR636##                                                                             [B'M'] .sub.n                                    ______________________________________                                         *Note: Oxygens always para on B'-                                        

EXAMPLE 37

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 58.035 g (0.23669 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 307.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 90.9 g of 85.4% H₃ PO₄ with 216.8 g of 115% PPA).When dehydrochlorination is substantially complete. 76.281 g (0.23669mol) of monomer 6b is added followed by the gradual addition of 163.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 17%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'J'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 38

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 54.581 g (0.25617 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 330.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.6 g of 85.4% H₃ PO₄ with 232.7 g of 115% PPA).When dehydrochlorination is substantially complete, 82.559 g (0.25617mol) of monomer 6b is added followed by the gradual addition of 176.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 16%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'K'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 39

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 73.126 g (0.25747 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 362.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 107.1 g of 85.4% H₃ PO₄ with 255.5 g of 115% PPA).When dehydrochlorination is substantially complete, 82.978 g (0.25747mol) of monomer 6b is added followed by the gradual addition of 185.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.0% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 15%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'L'].sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 37-39, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 24a. Thee→ denotes especially preferred selected monomer reactions.

                  TABLE 24a                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR637##                                                                    ##STR638##                                                                    Monomer (1,1) + Monomer (6,2)                                                                    ##STR639##                                                                             Polymer V(2)                                     ______________________________________                                         1d + 6b                                                                                          ##STR640##                                                                             [B'K'] .sub.n*                                    1e + 6b                                                                                          ##STR641##                                                                             [C'L'] .sub.n                                     1f + 6b                                                                                          ##STR642##                                                                             [C'K'] .sub.n                                     1g + 6b                                                                                          ##STR643##                                                                             [C'J'] .sub.n                                     1h + 6b                                                                                          ##STR644##                                                                             [B'N'] .sub.n                                    ______________________________________                                         *Note: Oxygens always para on B'-                                        

EXAMPLE 40

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 76.047 g (0.23369 mol) of monomer 1i is dehydrochlorinated inan "initial" solution of 369.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.1 g of 85.4% H₃ PO₄ with 260.1 g of 115% PPA).When dehydrochlorination is substantially complete, 58.269 g (0.23369mol) of monomer 6a is added followed by the gradual addition of 180.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --D'G'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 41

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1j is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 12% fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --D'H'].sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 42

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1k is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

--D'H']_(n)

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 43

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 101.996 g (0.25747 mol) of monomer 1l is dehydrochlorinatedin an "initial" solution of 493.3 g of PPA having a P₂ O₅ content of77.3% (prepared by mixing 145.7 g of 85.4% H₃ PO₄ with 347.6 g of 115%PPA). When dehydrochlorination is substantially complete, 63.385 g(0.25747 mol) of monomer 6a is added followed by the gradual addition of221.5 g of P₂ O₅. The mixture is then stirred and heated according to aschedule similar to Example 8. The amount of P₂ O₅ added is preselected(as determined accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --D'I'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 40-43, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 24b and24c. The e→and p→denote especially preferred and preferred selectedmonomer reactions respectively.

                  TABLE 24b                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR645##                                                                    ##STR646##                                                                    Monomer (1,2) + Monomer (6,1)                                                                    ##STR647##                                                                             Polymer V(2)                                     ______________________________________                                         1m + 6a                                                                                          ##STR648##                                                                             [D'M'] .sub.n                                     1n + 6a                                                                                          ##STR649##                                                                             [E'G'] .sub.n                                     1o + 6a                                                                                          ##STR650##                                                                             [E'H'] .sub.n                                     1p + 6a                                                                                          ##STR651##                                                                             [E'I'] .sub.n                                    ______________________________________                                    

                  TABLE 24c                                                       ______________________________________                                         Monomer (1,2) + Monomer (6,2)                                                                    ##STR652##                                                                             Polymer V(2)                                     ______________________________________                                         1i + 6b                                                                                          ##STR653##                                                                             [D'J'] .sub.n                                     1j + 6b                                                                                          ##STR654##                                                                             [D'K'] .sub.n*                                    1k + 6b                                                                                          ##STR655##                                                                             [D'K'] .sub.n**                                   1l + 6b                                                                                          ##STR656##                                                                             [D'L'] .sub.n                                     1m + 6b                                                                                          ##STR657##                                                                             [D'N'] .sub.n                                     1n + 6b                                                                                          ##STR658##                                                                             [E'J'] .sub.n                                     1o + 6b                                                                                          ##STR659##                                                                             [E'K'] .sub.n                                     1p + 6b                                                                                          ##STR660##                                                                             [E'L'] .sub.n                                    ______________________________________                                         *Note: Oxygen always in 3.3'-positions on                                     **Note: Oxygens always in 4,4'-positions on D'-                          

EXAMPLE 44

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 123.074 g (0.64042 mol) of monomer 9a is dissolved in an "initial"solution of 423.1 g of PPA having a P₂ O₅ content of 77.3% (prepared bymixing 125.0 g of 85.4% H₃ PO₄ with 298.1 g of 115% PPA). Whendissolution is substantially complete, an additional 223.0 g of P₂ O₅ isgradually added to the mixture and dissolved by stirring and heatingessentially according to Example 27. The amount of P₂ O₅ added ispreselected (as determined in accord with the aforementioned formulae a*and b*) to provide the reaction mixture with an effective P₂ O₅ contentof approximately 85.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'P'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 45

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 86.502 g (0.30457 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 468.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 141.3 g of 85.4% H₃ PO₄ with 337.0 g of 115% PPA).When dehydrochlorination is substantially complete. 79.864 g (0.30457mol) of monomer 7a is added followed by the gradual addition of 233.0 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'O'.sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 45, other Type VII extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration. P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 26 and27. The e→ denotes especially preferred selected monomer reactions.

                  TABLE 26                                                        ______________________________________                                        Polymers of Type VII, Class 1                                                 Polymerization Reactions:                                                      ##STR661##                                                                    ##STR662##                                                                    Monomer (1,1) + Monomer (7,1)                                                                    ##STR663##                                                                             Polymer VII(1)                                   ______________________________________                                         1e + 7a                                                                                          ##STR664##                                                                             [C'O'] .sub.n                                    ______________________________________                                    

                  TABLE 27                                                        ______________________________________                                        Polymers of Type VII, Class 2                                                 Polymerization Reactions:                                                      ##STR665##                                                                    ##STR666##                                                                    Monomer (1,2) + Monomer (7,1)                                                                    ##STR667##                                                                             Polymer VII(2)                                   ______________________________________                                         1l + 7a                                                                                          ##STR668##                                                                             [D'O'] .sub.n                                     1p + 7a                                                                                          ##STR669##                                                                             [E'O'] .sub. n                                   ______________________________________                                    

EXAMPLE 46

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 102.35 g (0.48036 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 329.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.3 g of 85.4% H₃ PO₄ with 231.9 g of 115% PPA).When dehydrochlorination is substantially complete, 67.296 g (0.48036mol) of monomer 8a is added followed by the gradual addition of 250.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 87.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'S'.sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 47

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 137.73 g (0.48494 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 370.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.6 g of 85.4% H₃ PO₄ with 261.3 g of 115% PPA).When dehydrochlorination is substantially complete, 67.939 g (0.48494mol) of monomer 8l a is added followed by the gradual addition of 263.5g of P₂ O₅. The mixture is then stirred and heated according to aschedule similar to Example 8. The amount of P₂ O₅ added is preselected(as determined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'Q'.sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 46 and 47, other Type VIII extendedchain polymers may be synthesized to yield liquid-crystallinecompositions having varying proportions of polymer concentration, P₂ O₅content and polymer intrinsic viscosity in accordance with the presentinvention.

The synthesis is illustrated by the reaction systems in Table 28. The e→and p→ denote especially preferred and preferred selected monomerreactions respectively.

                  TABLE 28                                                        ______________________________________                                        Polymers of Type VIII, Class 1                                                Polymerization Reactions:                                                      ##STR670##                                                                    ##STR671##                                                                    Monomer (1,1) + Monomer (8,1)                                                                    ##STR672##                                                                             Polymer VIII(1)                                  ______________________________________                                         1a + 8a                                                                                          ##STR673##                                                                             [B'R'] .sub.n                                     1d + 8a                                                                                          ##STR674##                                                                             [B'S' ] .sub.n                                    1e + 8a                                                                                          ##STR675##                                                                             [C'Q'] .sub.n                                     1f + 8a                                                                                          ##STR676##                                                                             [C'S'] .sub.n                                     1f + 8a                                                                                          ##STR677##                                                                             [C'R'] .sub.n                                     1h + 8a                                                                                          ##STR678##                                                                             [B'U'] .sub.n                                    ______________________________________                                    

EXAMPLE 48

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 140.33 (0.35423 mol) of monomer 1l is dehydrochlorinated inan "initial" solution of 313.01 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 92.5 g of 85.4% H₃ PO₄ with 220.5 g of 115% PPA).When dehydrochlorination is substantially complete, 49.627 g (0.35423mol) of monomer 8a is added followed by the gradual addition of 263.0 ofP₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --D'Q'.sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 49

A mixture of 123.38 g of 115% PPA and 52.63 g of concentratedorthophosphoric acid (85.7% H₃ PO₄) was stirred at 100° C. for 2 h underreduced pressure. After allowing the solution to cool to 50° C. under aflow of argon, a portion (168.18 g) of the PPA (77.3% P₂ O₅) was addedunder a flow of argon to a resin kettle containing 57.61082 g (0.23496mol, a₁ =0.95) of 1a that had been prepared as described in Example 8and 2.6358 g (0.012371 mol, a₂ =0.05) of 1b that had been prepared bythe method of Wolfe and Arnold, Macromolecules, Vol. 14, 909 (1981) andrecrystallized from hydrochloric acid containing 3 wt % of stannouschloride. The mixture was then stirred at 50° C. for 33h under reducedpressure and 90° C. for 4h under reduced pressure. Monomer 2a (41.0899g, 0.24733 mol=m, b₁ =1) was then added. The mixture was cooled toapproximately 40° C. and 139.18 g of P₂ O₅ was added to increase theeffective P₂ O₅ content before polymerization to 87.6%. The mixture wasthen stirred at the specified temperatures for the specified times undera flow of argon: 100° C. for 24h; 150° C. for 1h; 160° C. for 1h; 170°C. for 5.534 h ; and 200° C. for 64h. The final concentration of theresulting random copolymer was 16.8% in a PPA with an approximate P₂ O₅content of 82.5%. Fibers of the copolymer were isolated by drawing theresulting green, opalescent product and precipitating into water. Theintrinsic viscosity of the copolymer isolated after heating at 200° C.for 1.5 h was shown to be 25.4 dL/g and actually decreased to 24.4 dL/gafter completing the above heating schedule. The copolymer obtainedapparently is of the following structure: ##STR679## where the molefraction of AI units (a₁ b₁) is believed to be 0.95, the mole fractionof BI units (a₂ b₁) is believed to be 0.05, the average block lengthsy₁₁ and y₂₁ are believed to be 20 and 1, respectively, and the averagetotal number of recurring units of both types (n) is believed to beapproximately 100.

EXAMPLE 50

To a deaerated mixture of 16.09147 g (0.0656275 mol, a₁ =0.75) of 1a and4.66149 g (0.0218778 mol, a₂ =0.25) of 1b was added 220 g of freshlyprepared and deaerated PPA (The PPA was prepared from 173.81 g of 86.8%orthophosphoric acid and 267.64 g of phosphorous pentoxide,equilibrated, and deaerated). The mixture was stirred under an argonflow at: room temperature overnight; 50° C. for 3.5 h; and 72° C. for 21h. The mixture was stirred under reduced pressure at 72° C. overnight tosubstantially complete dehydrochlorination. Terephthalic acid (2a)(14.53762 g, 0.0875059 mol) was added to the solution and the mixturewas deaerated before stirring was initiated. The PPA prepared above wasthen added to this mixture to give a total of 394.5 g of PPA. The slurrywas then stirred under reduced pressure for 0.5 h at 110° C. and underan argon atmosphere at: 120° C. for 1h; 130° C. for 0.5 h; 140° C. for0.5 h; 150° C. for 0.5 h; 160° C. for 1.0 h; 170° C. for 15.5 h; 185° C.for 6.5 h; and 200° C. for 19h. The optically anisotropic productcontained 5.3 wt % polymer in PPA (84.0% P₂ O₅ content). Precipitationof a small amount of the polymeric product provided the randomcopolymer, believed to have the structure: ##STR680## where a₁ b₁ =0.75,y₁₁ =4, a₂ b₁ =0.25, and y₂₁ =1.33, with an intrinsic viscosity of 26.59dL/g in MSA at 30° C., which corresponds to an n value of approximately110.

EXAMPLE 51

To a deaerated mixture of 22.36319 g (0.0912061 mol, a₁ =0.9) of 1a and2.15918 g (0.0101340 mol, a₂ =0.10) of 1b was added approximately 230 gof freshly prepared deaerated PPA. (The PPA was prepared by stirring amixture of 135.97 g of 85.4% orthophosphoric acid and 207.36 g ofphosphorous pentoxide at 150° C. overnight under an argon atmosphere,followed by deaeration by stirring under reduced pressure at 150° C. for5.5 h. The solution was allowed to cool to room temperature under agronbefore use). The mixture was stirred under an argon flow at: roomtemperature overnight; 50° C. for 3h; and at 70° C. overnight. Thesolution was then stirred under reduced pressure for 2.5 h at 70° C.Terephthalic acid (2a) (16.83595 g, 0.101340 mol); was added to thesolution and, after placing the kettle under reduced pressure, stirringwas initiated. The remaining above-mentioned PPA was then added to themixture (total PPA added=317.6 g) under an argon atmosphere. Thepolymerization mixture was then stirred under an argon atmosphere at110° C. for 30 min; 120° C. for 30 min; 130° C. for 30 min; 140° C. for30 min; 150° C. for 30 min; 160° C. for 30 min; and 170° C. for 14.5h.The polymerization mixture was heated under an argon atmosphere withoutstirring at 185° C. for 5h and at 193°-200° C. for 28h. The finalpolymer concentration was 7.6 wt % in PPA (83.0% P₂ O₅). Precipitationof a small amount of the anisotropic polymer product provided the randomcopolymer of Type IX, Class 1 with the structure: ##STR681## where a₁ b₁=0.9, a₂ b₁ =0.10, and the average block lengths y₁₁ and y₂₁ arebelieved to be 10 and 1.11, respectively. The isolated copolymerpossessed an intrinsic viscosity of 26.36 dL/g in MSA at 30° C., whichcorresponds to an n value of approximately 110.

EXAMPLE 52

A solution of 135.51 g of 115% PPA and 59.10 g of 85.7% H₃ PO₄ wasstirred at 100° C. for 2h under reduced pressure. The solution wasallowed to cool to room temperature under reduced pressure, and 180.16 gof the mixture was added to 30.20054 g of 1a under an argon atmosphere.After a homogeneous mixture was obtained 28.29941 g (58.49995 g total,0.23859 mol total=m, a₁ =1) of deaerated 1a was added. The mixture wasstirred under reduced pressure at: 50° C. for 18.5 h; 70° C. for 10 min;80° C. for 25 min; and 90° C. for 5.5 h. Deaerated 2a (35.6892 g,0.21482 mol, b₁ =0.9) and 5.79905 g (0.02394 mol, b₂ =0.10) of deaerated4,4'-biphenyldicarboxylic acid (2aa) were added under an inertatmosphere. After the monomers were incorporated into the mixture, thereaction mixture was cooled to 40° C. and 138.11 g of deaerated P₂ O₅was added to give an effective P₂ O₅ content before polymerization of87.01%. After stirring at 100° C. for 63 h, the polymerization wasstirred at: 160° C. for 2.5 h; 170° C. for 5.5 h, and 200° C. for 64 h.The concentration of the resulting copolymer was 15.9% in PPA with a P₂O₅ content of approximately 82.5%. The reaction product wasstir-opalescent and was drawn into oriented fibers. The copolymerpossessed an intrinsic viscosity of 7.9 dL/g in MSA at 30° C. Thestructure of the resulting polymer is believed to be: ##STR682## wherea₁ b₁ is 0.9, a₁ b₂ is 0.1, y₁₁ is 10, y₁₂ is 1.1, and n isapproximately 40.

EXAMPLE 53

A mixture of 20.10 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 46.74 g of 115% PPA was stirred at 100° C. for 2 h under reducedpressure in a 100 mL 3-necked flask. After allowing this PPA solution,having a P₂ O₅ content of 77.3%, to cool to 50° C. under reducedpressure, a portion (82.45 g) was added under a flow of argon to a 200mL resin kettle containing 20.2783 g (0.082703 mol=m, a₁ =1) of 1a thathad been prepared and deaerated was described in Example 7. The mixturewas then stirred at the specified temperatures for the specified timesunder either reduced pressure (vac) or argon flow (Ar): 50° C. 4h, vac;50° C., 15h, Ar; 60° C., 3h, vac; 80° C., 1h, vac; 90° C., 3h, vac; 60°C., 15h, Ar; 80° C., 7h, vac. Trans-1,2-cyclohexanedicarboxylic acid (2gg) (0.6781 g, 0.004132 mol, b₂ =0.05) that as obtained from AldrichChemical Company and was recrystallized from methanol before use wasadded to the kettle and then terephthalic acid (2a) (13.05455 g,0.078579 mol, b₁ =0.95) was added. Powdered P₂ O₅ (45.00 g) was thenadded to the mixture that had been cooled to 50° C. to increase theeffective P₂ O₅ content before polymerization to 86.8%. The mixture wasthen stirred for 17h at 100° C. under an argon flow. The yellow mixturewas then heated with stirring under argon as follows: 120° C. for 1h;130°-140° C. for 1h; 150° C. for 2h; 160° C. for 0.5h; 170° C. for 4h(stir-opalescence was apparent during this time); 185° C. for 15.5h; and200° C. for 75h. The final concentration of the resulting randomcopolymer was 16.4% in PPA, with a P₂ O₅ content of approximately of82.2%. The polymer obtained apparently is of the following structure:##STR683## characterized as having an intrinsic viscosity inmethanesulfonic acid at 30° C. of 10.0 dL/g, which corresponds to anaverage n value of about 50, a mole fraction of --AI]_(n) units (a₁ b₁)of 0.95, and a mole fraction of --AA]"_(n) units (a₁ b₂) of 0.05. Theaverage block lengths, y₁₁ and y₁₂, are believed to be 20 and 1,respectively.

EXAMPLE 54

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer 1a and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR684##

EXAMPLE 55

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer 1b and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR685##

EXAMPLE 56

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR686##

EXAMPLE 57

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR687##

EXAMPLE 58

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR688##

EXAMPLE 59

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol% of monomer 2a and 50 mol% of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR689##

EXAMPLE 60

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2 Kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR690##

EXAMPLE 61

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR691##

EXAMPLE 62

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR692##

EXAMPLE 63

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR693##

EXAMPLE 64

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1c is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR694##

EXAMPLE 65

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 2a, and 5 mol % of monomer 2gg, 100 mol % ofmonomer 1a is substantially dehydrochlorinated in a comparable weightpercent of PPA with essentially similar P₂ O₅ content. After theaddition of 75 mol % of monomer 2a and 25 mol % of monomer 2e and anappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 12 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR695##

EXAMPLE 66

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol% of monomer 2a and 25 mol% of monomer 2eand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR696##

EXAMPLE 67

The procedure of Example 49 is essentially repeated. Instead of using 95mol% of monomer 1a, 5 mol% of monomer 1b, and 100 mol% of monomer 2a, amixture of 60 mol% of monomer 1a and 40 mol% of monomer 1i issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR697##

EXAMPLE 68

The procedure of Example 49 was essentially repeated. Instead of using95 mol% of monomer 1a, 5 mol% of monomer 1b, and 100 mol% of monomer 2a,a mixture of 80 mol% of monomer 1a and 20 mol% of monomer 1l wassubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture was then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed was anisotropic-liquid crystalline(exhibited stir-opalescence) and was formed into ordered fibers bysimple drawing. The copolymer obtained is believed to be of thefollowing structure: ##STR698##

EXAMPLE 69

The procedure of Example 69 is essentially repeated. Instead of using 95mol% of monomer 1a, 5 mol% of monomer 1b, and 100 mol% of monomer 2a, amixture of 85 mol% of monomer 1c and 15 mol% of monomer 1l issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR699##

EXAMPLE 70

The procedure of Example 52 is essentially repeated. Instead of using100 mol% of monomer 1a, 90 mol% of monomer 2a, and 10 mol% of monomer2aa, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2aaand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR700##

EXAMPLE 71

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2ggand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR701##

EXAMPLE 72

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2ffand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR702##

EXAMPLE 73

Two polymerizations (Step A and Step B) were conducted simultaneously inseparate resin kettles and combined at a later stage (Step C) to give aproduct of a block copolymer believed to have the following structure:##STR703## where a₁ b₁ is 0.793 and a₁ b₂ is 0.207 and y₁₁ is greaterthan about 30.

Step A: Preparation of --AI]_(n). A mixture of 92.06g of 115% PPA and39.45g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. A portion (128.63g) of the hotPPA (77.3% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 41.42682g (0.16896 mol) of 1a. The mixture was stirred at 50°C. under argon flow for 15h, then under reduced pressure at 60° C. for23.5h, 70° C. for 6h, and 80° C. for 8.5h to effect dehydrochlorination.Terephthalic acid (2a) (28.0688g, 0.16895 mol) was then added in fourportions. The mixture was cooled to approximately 40° C. and 92.22g ofP₂ O₅ was added. The mixture was stirred at the following temperaturesfor the specified times under a flow of argon: 100° C. for 42.5h; 120°C. to 160° C. in increments of 10° C. per 0.5h; 170° C. for 2.5h. Atthis time the mixture became stir-opalescent and a sample of the dopeexhibited birefringence under plane-polarized light. After an additional3h at 170° C. the polymer from Step B was added (See Step C). Theintrinsic viscosity of Polymer --AI]_(n) isolated from the reactionmixture immediately before Step C was 2.3 dL/g which corresponds to an nvalue (average number of recurring units) of 30 and a p value (extent ofreaction) of 0.983.

Step B: Preparation of --AG"]_(n). A mixture of 30.72g of 115% PPA and13.13g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. The PPA (41.66g; 77.3% P₂ O₅)was added without cooling under a flow of argon to a resin kettlecontaining 13.80877g (0.05632 mol) of 1a. The mixture was stirred at 50°C. under argon flow for 15h, then under reduced pressure at 60° C. for23.5h, 70° C. for 6h, and 80° C. for 35.5h. Isophthalic acid (2ss)(9.3569g, 0.05632 mol) that had been obtained from Aldrich ChemicalCompany in 99% purity was twice recrystallized from 90% aqueous ethanoland dried at 110° C. for 24h and was then added in two portionsincorporating the solid after each addition. The mixture was cooled toapproximately 40° C. and then 31.59g of P₂ O₅ was added. The mixture wasthen heated simultaneously and at the same heating schedule as thesolution in Step A.

Step C: Block Copolymerization. After 5.5h at 170° C., 72g of theviscous, red, optically isotropic product from Step B was added to thekettle from Step A under an argon atmosphere at the time indicated inStep A. Both kettles were heated under an argon flow as follows: 170° C.for 12.8h; 190° C. for 2h; 200° C. for 26h. The resulting mixtureremained stir-opalescent and continued to polymerize as indicated byintrinsic viscosities of samples removed at various times. Uponprecipitation in H₂ O, the final sample of the resulting copolymer hadan intrinsic viscosity of 17.5 dL/g in MSA at 30° C. The finalprecipitated sample of the portion of the product from Step B that hadnot been added to the product from Step A (but had been heated accordingto the same schedule as the mixture) had an intrinsic viscosity of 1.8dL/g in MSA at 30° C. The weight percent of polymer --AI]_(n) in theproduct from Step A was 16.2; the weight percent of polymer --AG"]_(n)in the product from Step B was 16.3. The weight percent of blockcopolymer ##STR704## was therefore calculated to be 16.2; the weightpercents of the individual --AI]_(n) and --AG"]_(n) segments of theblock copolymer in the final product were 12.9 and 3.4, respectively, ascalculated from the weights of the constituent polymers added and thetotal weight of the resulting product. The mol percent of mesogenic--AI]_(n) and flexible --AG"]_(n) units were 79.3 and 20.7,respectively, as calculated from the weights of the constituent polymersadded.

EXAMPLE 74

Two polymerizations were conducted simultaneously in separate resinkettles (Steps A and B), and combined at a later stage (Step C) to givea block polymer product believed to have the following structure:##STR705## where a₁ b₁ is 0.587 and a₁ b₂ is 0.413 and Y₁₁ is greaterthan about 40.

Step A: Preparation of --AI]_(n). A mixture of 36.73g of 115% PPA and24.43g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (58.69%) of thehot PPA (74.9% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 20.71434g (0.08448 mol) of 1a. The mixture was stirred underreduced pressure at 50° C. for 1h, 70° C. for 1.3h, and 80° C. for 23h.To dissolve monomer, 6.02g of P₂ O₅ was added, and the kettle was heatedat 80° C. for an additional 26h. Terephthalic acid (2a) (14.0351g,0.08448 mol) was then added in three portions. The acid monomer wasincorporated by stirring after each addition. The kettle was cooled to50° C. and an additional 46.24g deaerated P₂ O₅ was added. The mixturewas stirred under argon flow at the following temperatures for thespecified times: 100° C. for 18h; 150° C. for 2h; 170° C. for 5h. (After1h at 170° C. the mixture exhibited stir-opalescence). At this time thepolymer from Step B was added. (See Step C).

Step B: Preparation of --AN"]_(n) A mixture of 63.88g of 115% PPA and42.51g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (104.41g) of thePPA (74.9% P₂ O₅) was added without cooling under a flow of argon to aresin kettle containing 20.26865g (0.08266 mol) of 1a. The mixture wasstirred under reduced pressure at 50° C. for 0.8h, 60° C. for 7.5h, and80° C. for 9.5h. Sebacic acid, (monomer 2zz, purified by crystallizationof the disodium salt, then repeated recrystallization of the free acidin H₂ O and dried in vacuo at 80° C. for 24h) (16.7190g, 0.08266 mol),was then added in three portions to the resin kettle, incorporatingafter each addition. The mixture was cooled to 50° C. and 70.91g of P₂O₅ was added slowly. The polymerization proceeded rapidly, and thegellike solid was heated without stirring at 100° C. for 16.5h and at130° C. for 7.8h. At this time the polymer was removed in an inertatmosphere, leaving a portion in the kettle which was reassembled andheated according to the same schedule as the block copolymer.

Step C: Block Copolymerization. A portion of the polymer from Step B(153.13g) was added under an argon atmosphere to the kettle from Step A.The mixture was then stirred under argon flow at 170° C. for 16h and at200° C. for 28h. The mixture remained stir-opalescent and continued topolymerize as shown by an increase in the bulk viscosity. The weightpercent of polymer --AI]_(n) in the product from Step A was 16.1; theweight percent of polymer --AN"]_(n) in the product from Step B was12.1. The weight percent of block copolymer was calculated to be 12.1;the weight percents of --AI]_(n) and --AN"]_(n) segments of the blockcopolymer in solution were 6.8 and 5.6 respectively. The mole percent ofmesogenic --AI]_(n) and --AN"]_(n) units were 58.7 and 41.3respectively, as calculated from the weights of the constituent polymersadded. The resulting polymer isolated was not completely soluble inmethane sulfonic acid thus precluding intrinsic viscosity measurements.

EXAMPLE 75

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR706##

EXAMPLE 76

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR707##

EXAMPLE 77

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR708##

EXAMPLE 78

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR709##

EXAMPLE 79

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR710##

EXAMPLE 80

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homp-oligomers) of Examples 13 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR711##

EXAMPLE 81

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 16 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR712##

EXAMPLE 82

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR713##

EXAMPLE 83

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 18 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR714##

EXAMPLE 84

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR715##

EXAMPLE 85

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 19 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR716##

EXAMPLE 86

The procedure of Example 73 essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR717##

EXAMPLE 87

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR718##

EXAMPLE 88

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2ff are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubsantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR719##

EXAMPLE 89

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2xx are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR720##

EXAMPLE 90

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2uu are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR721##

EXAMPLE 91

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1q and2a are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockplymer obtained is of the followingstructure: ##STR722##

EXAMPLE 92

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in step B, equimolar quantities of monomers 1band 2ss are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and Bdiverted into a common agitated reaction vessel in amounts to give aratio of 1.5:1. The polymerization of the resultant mixture is allowedto continue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spining or drawing and the like. The blockpolymerobtained is of the following structure: ##STR723##

EXAMPLE 93

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2xx are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR724##

EXAMPLE 94

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2zz are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR725##

EXAMPLE 95

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3c is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR726##

EXAMPLE 96

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3d is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR727##

EXAMPLE 97

The procedure of Example 27 was essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3e was substantially dehydrochlorinated in a comparable weight percentof PPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture was then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed was anisotropic-liquidcrystalline (exhibit stir-opalescence), highly drawable, and could bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is believed to be of the following struccture:##STR728##

EXAMPLE 98

The Procedure of Example 73 is essentially repeated. Subsequent to thestart of polymeriztion and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 29 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR729##

EXAMPLE 99

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR730##

EXAMPLE 100

3,4-diaminobenzoic acid (3e) (Aldrich, 97%) was recrystallized from hotwater with 3-g of carbon black and 0.5 g of sodium dithionite added forevery 30 g of 3e. The recovered light orange crystals were dried at roomtemperature under reduced pressure for 24 h. An acid mixture preparedfrom 183.4 g of 115% PPA and 78.6 g of 85.7% H₃ PO₄ (J. T. BakerAnalyzed Reagent) was deaerated by heating in a 3-necked flask at 100°C. for 2 h under reduced pressure and then at 50° C. under reducedpressure for 17 h. To a 500 mL resin kettle was added 20.24 g of 3e. Thekettle was then deaerated by applying reduced pressure and then fillingwith nitrogen three times. 51.11 g of the above-mentioned PPA was addedto the kettle and the contents stirred until well mixed. 38.77 g of P₂O₅ (J. T. Baker Analyzed Reagent, 99.1%) was added. The temperature ofthe kettle was raised to 100° C. and the P₂ O₅ incorporated into themixture. The following heating schedule was used with color changes asnoted: 100° C. for 20 min; 110° C. for 20 min; 120° C. for 20 min; 130°C. for 20 min; color changed from tan to green; 140° C. for 20 min; thegreen color became darker. Reduced pressure was briefly applied whichcaused considerable foaming; 105° C. for 20 min; 160° C. for 20 min. Asample was removed and precipitated in water to give a red polymericsubstance with an intrinsic viscosity in MSA at 30.0° C. of 4.25 dL/g.Heating at 160° C. was continued for another 30 h. The intrinsicviscosity in MSA at 30° C. of polymer component of a sample removed atthis time was measured to be 4.5 dL/g. The reaction was heated at 175°C. an additional 35 h. The resultant red-brown polymeric materialisolated from this solution had an intrinsic viscosity of 4.5 dL/g inmethanesulfonic acid at 30.0° C. Final reaction product contained 16.8%of polymer --W]_(n) in PPA. Initial P₂ O₅ content was 77.3%, final P₂ O₅content was 82.2%.

EXAMPLE 101

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR731##

EXAMPLE 102

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR732##

EXAMPLE 103

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR733##

EXAMPLE 104

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubtantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR734##

EXAMPLE 105

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completd) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR735##

EXAMPLE 106

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR736##

EXAMPLE 107

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temparature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR737##

EXAMPLE 108

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR738##

EXAMPLE 109

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR739##

EXAMPLE 110

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR740##

EXAMPLE 111

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR741##

EXAMPLE 112

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spining or drawingand the like. The blockpolymer obtained is of the following structure:##STR742##

EXAMPLE 113

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 19 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR743##

EXAMPLE 114

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 23 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR744##

EXAMPLE 115

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 22 and 27 are diverted into a commonagitated reaction of vessel in amounts to give a ratio of 1:2. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR745##

                  APPENDIX                                                        ______________________________________                                        General Structure Reference                                                   ______________________________________                                        [A]                                                                           [B]                                                                                       ##STR746##                                                        [C]                                                                                       ##STR747##                                                        [D]                                                                                       ##STR748##                                                        [E]                                                                                       ##STR749##                                                        [F]                                                                                       ##STR750##                                                        [G]                                                                                       ##STR751##                                                        [H]                                                                                       ##STR752##                                                        [I]                                                                                       ##STR753##                                                        [J]                                                                                       ##STR754##                                                        [K]                                                                                       ##STR755##                                                        [L]                                                                                       ##STR756##                                                        [M]                                                                                       ##STR757##                                                        [N]                                                                                       ##STR758##                                                        [O]                                                                                       ##STR759##                                                        [P]                                                                                       ##STR760##                                                        [Q]                                                                                       ##STR761##                                                        [R]                                                                                       ##STR762##                                                        [S]                                                                                       ##STR763##                                                        [T]                                                                                       ##STR764##                                                        [U]                                                                                       ##STR765##                                                        [V]                                                                                       ##STR766##                                                        [W]                                                                                       ##STR767##                                                        [X]                                                                                       ##STR768##                                                        [Y]                                                                                       ##STR769##                                                        [Z]                                                                                       ##STR770##                                                        [A']                                                                                      ##STR771##                                                        [B']                                                                                      ##STR772##                                                        [C']                                                                                      ##STR773##                                                        [D']                                                                                      ##STR774##                                                        [E']                                                                                      ##STR775##                                                        [F']                                                                                      ##STR776##                                                                    ##STR777##                                                        [G']                                                                                      ##STR778##                                                                    ##STR779##                                                        [H']                                                                                      ##STR780##                                                        [I']                                                                                      ##STR781##                                                                    ##STR782##                                                         [J']                                                                                     ##STR783##                                                                    ##STR784##                                                                    ##STR785##                                                         [K']                                                                                     ##STR786##                                                                    ##STR787##                                                         [L']                                                                                     ##STR788##                                                                    ##STR789##                                                        [M']                                                                                      ##STR790##                                                                    ##STR791##                                                         [N']                                                                                     ##STR792##                                                                    ##STR793##                                                        [O']                                                                                      ##STR794##                                                        [P']                                                                                      ##STR795##                                                        [Q']                                                                                      ##STR796##                                                        [R']                                                                                      ##STR797##                                                        [S']                                                                                      ##STR798##                                                        [T']                                                                                      ##STR799##                                                        [U']                                                                                      ##STR800##                                                        [V']                                                                                      ##STR801##                                                        [W']                                                                                      ##STR802##                                                        [X']                                                                                      ##STR803##                                                        [ Y']                                                                                     ##STR804##                                                        [Z']                                                                                      ##STR805##                                                        [A"]                                                                                      ##STR806##                                                        [B"]                                                                                      ##STR807##                                                        [C"]                                                                                      ##STR808##                                                        [D"]                                                                                      ##STR809##                                                        [E"]                                                                                      ##STR810##                                                        [F"]                                                                                      ##STR811##                                                        [G"]                                                                                      ##STR812##                                                        [H"]                                                                                      ##STR813##                                                        [I"]                                                                                      ##STR814##                                                        [J"]       (CH.sub.2 ) .sub.2                                                 [K"]       (CH.sub.2 ) .sub.3                                                 [L"]       (CH.sub.2 ) .sub.4                                                 [M"]       (CH.sub.2 ) .sub.5                                                 [N"]       (CH.sub.2 ) .sub.8                                                 [O"]                                                                                      ##STR815##                                                        [P"]                                                                                      ##STR816##                                                        [Q"]                                                                                      ##STR817##                                                        [R"]                                                                                      ##STR818##                                                        [S"]                                                                                      ##STR819##                                                        [T"]                                                                                      ##STR820##                                                        [U"]                                                                                      ##STR821##                                                        [V"]                                                                                      ##STR822##                                                        [W"]                                                                                      ##STR823##                                                        [X"]                                                                                      ##STR824##                                                        [Y"]                                                                                      ##STR825##                                                        [Z"]                                                                                      ##STR826##                                                        ______________________________________                                    

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above except insofar as they are defined inthe following claims.

What we claim is:
 1. A novel polymer composition of workable viscositywhich is useful as a dope in the production of fibers and filmscomprising a liquid crystalline polymer solution of polyphosphoric acidscontaining at least one high molecular weight extended chain polymerhaving one or more mesogenic group or groups, said extended chainpolymer(s) having a molecular weight of at least 10,000 as determined byintrinsic viscosity and being present in sufficient concentration so asto produce a liquid crystalline polymer phase in said solution, with theproviso that when the polymer ispoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) that saidpoly([benzo-(1,2-d:4,5-d')-bisthiazole-2,6-diyl]-1,4-phenylene) polymerconcentration be greater than 10 percent by weight based on the totalweight of said composition and that the molecular weight of saidpoly([benzo-(1,2-d:4,5-d') bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity of at least about 12 dL/g asdetermined in methanesulfonic acid at 30° C.
 2. A novel polymercomposition of workable viscosity which is useful as a dope in theproduction of fibers and films comprising a liquid crystalline polymersolution of polyphosphoric acids and at least one high molecular weightextended chain polymer having one or more mesogenic group or groups,said extended chain polymer(s) being present in sufficient concentrationso as to produce a liquid crystalline polymer phase in said solution,with the proviso that when said extended chain polymer is a homopolymerthat said homopolymer is other than Poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene).
 3. A composition according toclaim 2, wherein said composition is capable of being spun at high drawratios.
 4. A composition according to claim 2, wherein said compositionis characterized as having a phosphorus pentoxide content within therange from about 82% to about 86% by weight on the total weight of saidpolyphosphoric acids.
 5. A composition according to claim 1, whereinsaid composition is capable of being spun at high draw ratios.
 6. Acomposition according to claim 1, wherein said composition ischaracterized as having a phosphorus pentoxide content within the rangefrom about 82 percent to about 86 percent by weight based on the totalweight of said polyphosphoric acids.
 7. A composition according to claim1, 5, or 6, wherein said extended chain polymer includes at least onehomopolymer having the general formulas: ##STR827## wherein Ar¹ is##STR828## X₁ and X₅ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another and Y² is nil or is##STR829## n being a positive integer; ##STR830## wherein Ar³ is##STR831## X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atom and X₃ being bonded to aromatic carbon atomsof Ar³, N and X₃ of each hetero ring are disposed ortho to one another,n being a positive integer; ##STR832## wherein Ar¹ is ##STR833## and Ar⁴is ##STR834## the nitrogen atoms being bonded to aromatic carbon atomsof Ar¹ and the carbon atoms being bonded to aromatic carbon atoms ofAr⁴, n being a positive integer; ##STR835## wherein Ar⁵ is ##STR836##the nitrogen atoms being bonded to Ar⁵, n being a positive integer;##STR837## wherein Ar⁶ is ##STR838## Ar¹ represents a different aromaticmoiety and is ##STR839## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₄ and X₅ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ or each hetero ring are disposed ortho to oneanother, n being a positive integer; ##STR840## wherein Ar⁹ is##STR841## X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH group and X₄ being bonded to aromatic carbon atoms ofAr⁹, n being a positive integer; ##STR842## wherein Ar¹ is ##STR843## Y⁷is ##STR844## the nitrogen atoms being bonded to aromatic carbon atomsof Ar¹ and bonded to adjacent carbon atoms of Y⁷, n being a positiveinteger; or ##STR845## wherein Ar¹ is ##STR846## Y⁸ is ##STR847## X₁ andX₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹ and adjacent carbon atoms of Y⁸,N and X₁ and X₂ of each hetero ring are disposed ortho to one another, nbeing a positive integer.
 8. A composition according to claim 1, 5, or6, wherein said extended chain polymer includes at least one homopolymerhaving the general formula: ##STR848## wherein Ar¹ is ##STR849## X₁ andX₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another and Y² is nil or is ##STR850## nbeing a positive integer.
 9. A composition according to claim 1, 3, 4,or 2 wherein said extended chain polymer is a homopolymer having thegeneral formulas: ##STR851## wherein Ar³ is ##STR852## X₃ is sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomand X₃ being bonded to aromatic carbon atoms or Ar³, N and X₃ of eachhetero ring are disposed ortho to one another, n being a positiveinteger; ##STR853## wherein Ar¹ is ##STR854## and Ar⁴ is ##STR855## thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and thecarbon atoms being bonded to aromatic carbon atoms of Ar⁴, n being apositive integer; ##STR856## wherein Ar⁵ is ##STR857## the nitrogenatoms being bonded to Ar⁵, n being a positive integer; ##STR858##wherein Ar⁶ is ##STR859## Ar¹ represents a different aromatic moiety andis ##STR860## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH groups andX₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH andX₁ or X₂ of each hetero ring are disposed ortho to one another, n beinga positive integer; ##STR861## wherein Ar⁹ is ##STR862## X₄ is sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH group andX₄ being bonded to aromatic carbon atoms of Ar⁹, n being a positiveinteger; ##STR863## wherein Ar¹ is ##STR864## Y⁷ is ##STR865## thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer; or##STR866## wherein Ar¹ is ##STR867## Y⁸ is ##STR868## X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹ and adjacent carbon atoms of Y⁸ N and X₁ orX₂ of each hetero ring are disposed ortho to one another, n being apositive integer.
 10. A composition according to claim 1, 3, 4, or 2wherein said extended chain polymer is a homopolymer the generalformula: ##STR869## wherein Ar³ is ##STR870## X₃ is sulfur, oxygen, orNR (R being hydrogen or an organic group), the nitrogen atom and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, n being a positive integer. 11.A composition according to claim 7 wherein said extended chain polymeris a homopolymer having the general formula: ##STR871## wherein Ar¹ is##STR872## and Ar⁴ is ##STR873## the nitrogen atoms being bonded toaromatic carbons atoms of Ar¹ and the carbon atoms being bonded toaromatic carbon atoms of Ar⁴, n being a positive integer.
 12. Acomposition according to claim 7 wherein said extended chain polymer isa homopolymer having the general formula: ##STR874## wherein Ar⁵ is##STR875## the nitrogen atoms being bonded to Ar⁵, n being a positiveinteger.
 13. A composition according to claim 7 wherein said extendedchain polymer is a homopolymer having the general formula: ##STR876##wherein Ar⁶ is ##STR877## Ar¹ represents a different aromatic moiety andis ##STR878## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH groups andX₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH andX₁ or X₂ of each hetero ring are disposed ortho to one another, n beinga positive integer.
 14. A composition according to claim 7 wherein saidextended chain polymer is a homopolymer having the general formula:##STR879## wherein Ar⁹ is ##STR880## X₄ is sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the NH group and X₄ being bonded toaromatic carbon atoms of Ar⁹, n being a positive integer.
 15. Acomposition according to claim 7 wherein said extended chain polymer ishomopolymer having the general formula: ##STR881## wherein Ar¹ is##STR882## Y⁷ is ##STR883## the nitrogen atoms being bonded to aromaticcarbon atoms of Ar¹ and bonded to adjacent carbon atoms of Y⁷, n being apositive integer.
 16. A composition according to claim 7 wherein saidextended chain polymer is a homopolymer having the general formula:##STR884## wherein Ar¹ is ##STR885## Y⁸ is ##STR886## X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹ and adjacent carbon atoms of Y⁸ N and X₁ orX₂ of each hetero ring are disposed ortho ot one another, n being apositive integer.
 17. A composition of claim 7, wherein said polymer isa formula I extended chain homopolymer having the formula: ##STR887##wherein n is greater than
 60. 18. A composition of claim 7, wherein saidpolymer is a formula I extended chain homopolymer having the formula:##STR888## wherein n is greater than
 110. 19. A composition of claim 7,wherein said polymer is a formula I extended chain homopolymer havingthe formula: ##STR889## wherein n is greater than
 70. 20. A compositionof claim 7, wherein said polymer is a formula I extended chainhomopolymer having the formula: ##STR890## wherein n is greater than 60.21. A composition of claim 7, wherein said polymer is a formula Iextended chain homopolymer having the formula: ##STR891## wherein n isgreater than
 60. 22. A composition of claim 1, or 2 wherein said polymeris a formula II extended chain homopolymer having the formula:##STR892## wherein n is greater than
 60. 23. A composition of claim 1,or 2 wherein said polymer is a formula II extended chain homopolymerhaving the formula: ##STR893## wherein n is greater than
 60. 24. Acomposition of claim 11, wherein said polymer is a formula III extendedchain homopolymer having the formulas: ##STR894## wherein n is greaterthan
 50. 25. A composition of claim 11, wherein said polymer is aformula III extended chain hompolymer having the formulas: ##STR895##wherein n is greater than
 60. 26. A composition of claim 11, whereinsaid polymer is a formula IV extended chain homopolymer having theformula: ##STR896## wherein n is greater than
 70. 27. A composition ofclaim 13, wherein said polymer is a formula V extended chain homopolymerhaving the formulas: ##STR897## wherein n is greater than
 30. 28. Acomposition of claim 13, wherein said polymer is a formula V extendedchain homopolymer having the formulas: ##STR898## wherein n is greaterthan
 30. 29. A composition of claim 13, wherein said polymer is aformula V extended chain homopolymer having the formula: ##STR899##wherein n is greater than
 30. 30. A composition of claim 14, whereinsaid polymer is a formula VI extended chain homopolymer having theformula: ##STR900## wherein n is greater than
 30. 31. A composition ofclaim 15, wherein said polymer is a formula VII extended chainhomopolymer having the formula: ##STR901## wherein n is greater than 30.32. A composition of claim 16, wherein said polymer is a formula VIIIextended chain homopolymer having the formulas: ##STR902## wherein n isgreater than
 40. 33. A composition of claim 16, wherein said polymer isa formula VIII extended chain homopolymer having the formula: ##STR903##wherein n is greater than
 30. 34. A composition according to claim 1, 3,4, or 2, wherein said extended chain polymer includes at least onecopolymer having the general formulas: ##STR904## wherein Ar¹ is##STR905## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another, and Y² is nil or is##STR906## a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said copolymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;##STR907## wherein Ar¹ is ##STR908## X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atomsof Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR909## a_(i) b_(j) m/m+m' represents themolar proportions of the respective different recurring units present insaid copolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar³represents a different aromatic moiety and is ##STR910## the nitrogenatom and X₃ being bonded to aromatic carbon atoms of Ar³, c_(k) m'/m+m'represents the molar proportions of the respective different recurringunits present in said copolymer, y_(k) represents an average number ofthe respective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR911## wherein Ar³ is##STR912## X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atom and X₃ being bonded to aromatic carbon atomsof Ar³, N and X₃ of the hetero ring are disposed ortho to one another,c_(k) represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(k) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, n being a positive integer; ##STR913## wherein Ar¹ is##STR914## Ar⁴ is ##STR915## the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR916## wherein Ar⁴ is ##STR917## Ar¹ is##STR918## and Ar⁵ is ##STR919## the carbon atoms being bonded to Ar⁴and Ar⁵ and the nitrogen atoms being bonded to Ar¹ and Ar⁵, n being apositive integer; c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, a_(i) b_(j) m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR920## wherein Ar¹ representsan aromatic moiety and is ##STR921## Ar⁶ represents a different aromaticmoiety and is ##STR922## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer; ##STR923##wherein Ar⁶ represents an aromatic moiety and is ##STR924## Ar¹represents a different aromatic moiety and is ##STR925## X₁ and X₂ arethe same or different and are sulfur, oxygen,or NR (R being hydrogen oran organic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹, NH and X¹ or X² of each hetero ring aredisposed ortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar⁹represents an aromatic moiety different from Ar⁶ and Ar¹ and is##STR926## X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH group and X₄ being bonded to aromatic carbon atoms of Ar⁶and Ar⁹, C_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;or ##STR927## wherein Ar¹ is ##STR928## Y⁷ is ##STR929## the nitrogenatoms being bonded to aromatic carbon atoms of Ar¹ and bonded toadjacent carbon atoms of Y⁷, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer.
 35. A composition according to claim 1 of 2 whereinsaid extended chain polymer is a copolymer having the general formula:##STR930## wherein Ar¹ is ##STR931## X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the nitrogen atoms and X₁ an d X₂ being bonded to aromatic carbon atomsof Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, and Y² is nil or is ##STR932## a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer.
 36. A composition according to claim 1 or 2 whereinsaid extended chain polymer is a copolymer having the general formula:##STR933## wherein Ar³ is ##STR934## X₃ is sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the nitrogen atom and X₃ beingbonded to aromatic carbon atoms of Ar³, N and X₃ of the hetero ring aredisposed ortho to one another, c_(k) represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(k) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger.
 37. A composition according to claim 1 or 2 wherein saidextended chain polymer is a copolymer having the general formula:##STR935## wherein Ar¹ is ##STR936## X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atomsof Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR937## a_(i) b_(j) m/m+' represents themolar proportions of the respective different recurring units present insaid copolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar³ is##STR938## the nitrogen atom and X₃ being bonded to aromatic carbonatoms of Ar³, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer.38. A composition according to claim 1 or 2 wherein said extended chainpolymer is a copolymer having the general formula: ##STR939## whereinAr¹ is ##STR940## Ar⁴ is ##STR941## the nitrogen atoms being bonded toAr¹ and the carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid copolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer.
 39. A composition according to claim 1 or 2 whereinsaid extended chain polymer is a copolymer having the general formula:##STR942## wherein Ar⁴ is ##STR943## Ar¹ is ##STR944## and Ar⁵ is##STR945## the carbon atoms being bonded to Ar⁴ and Ar⁵ and the nitrogenatoms being bonded to Ar¹ and Ar⁵, n being a positive integer; c_(k)m'/m+m' represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(k) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, a_(i) b_(j) m/m+m' represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger.
 40. A composition according to claim 1 or 2 wherein saidextended chain polymer is a copolymer having the general formula:##STR946## wherein Ar¹ is ##STR947## Ar⁶ represents a different aromaticmoiety and is ##STR948## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer.
 41. A compositionaccording to claim 1 or 2 wherein said extended chain polymer is acopolymer having the general formula: ##STR949## wherein Ar⁶ representsan aromatic moiety and is ##STR950## Ar¹ represents a different aromaticmoiety and is ##STR951## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X¹ or X² of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said copolymer, Ar⁹ represents an aromaticmoiety different from Ar⁶ and Ar¹ and is ##STR952## X₄ is sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH group andX₄ being bonded to aromatic carbon atoms of Ar⁶ and Ar⁹, c_(k) m/m+m'represents the molar proportions of the respective different recurringunits present in said copolymer, y_(k) represents an average number ofthe respective different sequential recurring units present in saidcopolymer, n being a positive integer.
 42. A composition according toclaim 1 or 2 wherein said extended chain polymer is a copolymer havingthe general formula: ##STR953## wherein Ar¹ is ##STR954## Y⁷ is##STR955## the nitrogen atoms being bonded to aromatic carbon atoms ofAr¹ and bonded to adjacent carbon atoms of Y⁷, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer.
 43. A composition of claim 35,wherein said extended chain polymer includes at least one copolymerhaving the formulas: ##STR956## wherein a₁ b₁ and a₁ b₂ or a₂ b₁ are thesaid molar proportions of the respective different recurring units, a₁b₁ being between zero and about one, a₁ b₂ or a₂ b₁ being equal to 1-a₁b₁ ; wherein y₁₁ and y₁₂ or y₂₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout one and less than about 75, y₁₂ or y₂₁ being greater than one andless than about 75, n being an average number of total recurring unitsgreater than about 50 and less than about 150; and said copolymer beingpresent in said composition in an amount greater than about 7 weightpercent.
 44. A composition of claim 35, wherein said extended chainpolymer includes at least one copolymer having the formula: ##STR957##wherein a₁ b₁ and a₁ b₂ are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ being between about 0.9 and one, a₁ b₂being equal to 1-a₁ b₁ ; wherein y₁₁ and y₁₂ are the said average numberof the respective different sequential recurring units, y₁₁ being atleast about 10, y₁₂ being about one, n being at least about 50 and lessthan about 150; and said copolymer being present in said composition inan amount greater than about 7 weight percent.
 45. A composition ofclaim 35, wherein said extended chain polymer includes at least onecopolymer having the formula: ##STR958## wherein a₁ b₁ and a₁ b₂ are thesaid molar proportions of the respective different recurring units, a₁b₁ being between about 0.95 and 1 a₁ b₂ being equal to 1-a₁ b₁ ; whereiny₁₁ different sequential recurring units, y₁₁ being at least about 20,y₁₂ being about one, n being at least about 50 and less than about 150;and said copolymer being present in said composition in an amountgreater than about 10 weight percent.
 46. A composition of claim 35,wherein said extended chain polymer includes at least one copolymerhaving the formula: ##STR959## wherein a₁ b and a₁ b₁ are the said molarproportions of the respective different recurring units, a₁ b₁ beingbetween about 0.9 and one, a₁ b₂ being equal to 1-a₁ b₁ ; wherein y₁₁and y₁₁ different sequential recurring units, y₁₁ being at least about10, y₁₂ being about one, n being at least about 50 and less than about100; and said copolymer being present in said composition in an amountgreater than about 12 weight percent.
 47. A composition of claim 35,wherein said extended chain polymer includes at least one copolymerhaving the formula: ##STR960## wherein a₁ b₁ and a₁ b₂ are the saidmolar proportions of the respective different recurring units, a₁ b₁being between about 0.95 and one, a₁ b₂ being equal to 1-a₁ b₁ ; whereiny₁₁ and y₁₂ are the said average number of the respective differentsequential recurring units, y₁₁ being at least about 20, y₁₂ being aboutone, n being at least about 50 and less than about 100; and saidcopolymer being present in said composition in an amount greater thanabout 12 weight percent.
 48. A composition of claim 35, wherein saidextended chain polymer includes at least one copolymer having theformula: ##STR961## wherein a₁ b₁ and a₁ b₂ are the said molarproportions of the respective different recurring units, a,₁ b₁ beingbetween about 0.9 and one, a₁ b₂ being equal to 1-a₁ b₁ ; wherein y₁₁and y₁₂ are the said average number of the respective differentsequential recurring units, y₁₁ being at least about 10, y₁₂ being aboutone, u being at least about 50 and less than about 150; and saidcopolymer being present in said composition in an amount greater thanabout 15 weight percent.
 49. A composition of claim 36, wherein saidextended chain polymer includes at least one copolymer having theformulas: ##STR962## wherein c₁ and c₂ are the said molar proportions ofthe respective different recurring units, c₁ being between about 0.75and one, c₂ being equal to 1-c₁ ; wherein y₁ and y₂ are the said averagenumber of the respective different sequential recurring units, y₁ beingat least about 4, y₂ being about 1.3, n being at least about 50 and lessthan about 200; and said copolymer being present in said composition inan amount greater than about 18 weight percent.
 50. A composition ofclaim 34, wherein said extended chain polymer includes at least onecopolymer having the formulas: ##STR963##
 51. A composition of claim 34,wherein said extended chain polymer includes at least one copolymerhaving its formulas: ##STR964##
 52. A composition according to claim 1,3, 4, or 2 wherein said extended chain polymer includes at least oneblock polymer having the general formulas: ##STR965## wherein A¹ is##STR966## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another and Y² is nil or is##STR967## a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; ##STR968## wherein Ar³ is ##STR969## X₃ is sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomand X₃ being bonded to aromatic carbon atoms of Ar³, N and X₃ of thehetero ring are disposed ortho to one another, c_(k) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR970## wherein Ar¹ is ##STR971## X₁ and X₂are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another and Y² is nil or is ##STR972##a_(i) b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said block polymer, Ar³ is ##STR973## X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₃ being bonded to aromatic carbon atom of Ar³, N andX₃ the hetero ring are disposed ortho to one another, c_(k) m'/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(k) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive interger; ##STR974## wherein Ar¹ is##STR975## Ar⁴ is ##STR976## the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR977## wherein Ar¹ is ##STR978## whenbonded to nitrogen atoms; and when Ar¹ is bonded to both nitrogen atomsand X₁ and X₂, Ar¹ is ##STR979## Ar⁴ is ##STR980## the nitrogen atomsbeing bonded to Ar¹ and the carbon atoms being bonded to Ar⁴, m'/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y' represents an average number ofthe respective different sequential recurring units present in saidblock polymer,X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ orX₂ of each hetero ring are disposed ortho to one another and Y² is nilor is ##STR981## m/m+m' represents the molar proportions of therespective different recurring units present in said block polymer, yrepresents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR982## wherein Ar³ is ##STR983## X₃ is sulfur, oxygen, orNR (R being hydrogen or an organic group), the nitrogen atom and X₃being bonded to aromatic carbon atoms of Ar, N and X₃ of the hetero ringare disposed ortho to one another, P represents the molar proportions ofthe respective different recurring units present in said block polymer,y'/2 represents an average number of the respectie different sequentialrecurring units present in said block polymer, Ar¹ is ##STR984## Ar⁴ is##STR985## the nitrogen atoms being bonded to Ar¹ and the carbon atomsbeing bonded to Ar⁴, q represents the molar proportions of therespective different recurring units present in said block polymer, yrepresents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR986## wherein Ar⁴ is ##STR987## Ar¹ is ##STR988## and Ar⁵is ##STR989## the carbon atoms being bonded to Ar⁴ and Ar⁵, and thenitrogen atoms being bonded to Ar¹ and Ar⁵, n being a positive integer;c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR990## wherein Ar¹ is##STR991## Ar⁶ represents a different aromatic moiety and is ##STR992##X₁ and X₂ are the same or different and are sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the NH groups and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of eachhetero ring are disposed ortho to one another, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y_(ij) represents an average number ofthe respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR993## wherein Ar¹ is##STR994## Ar⁶ is ##STR995## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, Ar⁹ representsan aromatic moiety different from Ar⁶ and Ar¹ and is ##STR996## X₄ issulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroup and X₄ being bonded to aromatic carbon atoms of Ar⁶ and Ar⁹,ckm'/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(k) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer; or ##STR997##wherein Ar¹ is ##STR998## Y⁷ is ##STR999## the nitrogen atoms beingbonded to aromatic carbon atoms of Ar¹ and bonded to adjacent carbonatoms of Y⁷, a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.
 53. A composition according to claim 1 or 2 whereinsaid extended chain polymer is a block polymer having the generalformula: ##STR1000## wherein Ar¹ is ##STR1001## X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or is ##STR1002## a_(i)b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 54. Acomposition according to claim 1 or 2 wherein said extended chainpolymer is a block polymer having the general formula: ##STR1003##wherein Ar³ is ##STR1004## X₃ is sulfur, oxygen, or NR (R being hydrogenor an organic group), the nitrogen atom and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of the hetero ring are disposed ortho toone another, c_(k) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger.
 55. A composition according to claim 1 or 2 wherein saidextended chain polymer is a block polymer having the general formula:##STR1005## wherein Ar¹ is ##STR1006## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbonatoms of Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho toone another and Y² is nil or is ##STR1007## a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar³ is ##STR1008## X₃ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₃ being bonded toaromatic carbon atom of Ar³, N and X₃ of the hetero ring are disposedortho to one another, c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer;
 56. A composition according to claim 1 or 2 whereinsaid extended chain polymer is a block polymer having the generalformula: ##STR1009## wherein Ar¹ is ##STR1010## Ar⁴ is ##STR1011## thenitrogen atoms being bonded to Ar¹ and the carbon atoms being bonded toAr⁴, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger.
 57. A composition according to claim 1 or 2 wherein saidextended chain polymer is a block polymer having the general formula:##STR1012## wherein Ar¹ is ##STR1013## when bonded to nitrogen atoms;and when Ar¹ is bonded to both nitrogen atoms and X₁ and X₂, Ar¹ is##STR1014## Ar⁴ is ##STR1015## the nitrogen atoms being bonded to Ar¹and the carbon atoms being bonded to Ar⁴, m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y' represents an average number of the respectivedifferent sequential recurring units present in said block polymer,X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another and Y² is nil or is ##STR1016##m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer.
 58. A compositionaccording to claim 1 or 2 wherein said extended chain polymer is a blockpolymer having the general formula: ##STR1017## wherein Ar³ is##STR1018## X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atom and X₃ being bonded to aromatic carbon atomsof Ar³, N and X₃ of the hetero ring are disposed ortho to one another, Prepresents the molar proportions of the respective different recurringunits present in said block polymer, y'/2 represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar¹ is ##STR1019## Ar⁴ is ##STR1020## the nitrogen atomsbeing bonded to Ar¹ and the carbon atoms being bonded to Ar⁴, qrepresents the molar proportions of the respective different recurringunits present in said block polymer, y represents an average number ofthe respective different sequential recurring units present in saidblock polymer, n being a positive integer.
 59. A composition accordingto claim 1 or 2 wherein said extended chain polymer is a block polymerhaving the general formula: ##STR1021## wherein Ar⁴ is ##STR1022## Ar¹is ##STR1023## and Ar⁵ is ##STR1024## the carbon atoms being bonded toAr⁴ and Ar⁵, and the nitrogen atoms being bonded to Ar¹ and Ar⁵, n beinga positive integer; c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 60. Acomposition according to claim 1 or 2 wherein said extended chainpolymer is a block polymer having the general formula: ##STR1025##wherein Ar¹ is ##STR1026## Ar⁶ represents a different aromatic moietyand is ##STR1027## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH groups andX₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH andX₁ or X₂ of each hetero ring are disposed ortho to one another, a_(i)b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 61. Acomposition according to claim 1 or 2 wherein said extended chainpolymer is a block polymer having the general formula: ##STR1028##wherein Ar¹ is ##STR1029## Ar⁶ is ##STR1030## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₁ and X₂ being bonded to aromatic carbonatoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hetero ring are disposedortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, Ar⁹represents an aromatic moiety different from Ar⁶ and Ar¹ and is##STR1031## X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH group and X₄ being bonded to aromatic carbon atoms of Ar⁶and Ar⁹, ckm'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger.
 62. A composition according to claim 1 or 2 wherein saidextended chain polymer is a block polymer having the general formula:##STR1032## wherein Ar¹ is ##STR1033## Y⁷ is ##STR1034## the nitrogenatoms being bonded to aromatic carbon atoms of Ar¹ and bonded toadjacent carbon atoms of Y⁷, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer.
 63. A composition of claim 53, wherein saidextended chain polymer includes at least one block polymer having theformulas: ##STR1035## wherein a₁ b₁, a₁ b₂, a₂ b₁, and a₂ b₂ are thesaid molar proportions of the respective different recurring units, a₁b₁ being between zero and one, a₁ b₂ or a₂ b₁ or a₂ b₂ being equal to1-a₁ b₁ ; wherein y₁₁, y₁₂, y₂₁, and y₂₂ are the said average number ofthe respective different sequential recurring units, y₁₁ being greaterthan about 20 and less than about 75, y₁₂ or y₂₁ or y₂₂ being greaterthan one and less than about 75, n being an average number of totalrecurring units greater than about 50 and less than about 150; and saidblock polymer being present in said composition in an amount greaterthan about 7 weight percent.
 64. A composition of claim 53, wherein saidextended chain polymer includes at least one block polymer having theformulas: ##STR1036## wherein a₁ b₁ and a₂ b₁ are the said molarproportions of the respective different recurring units, a₁ b₁ beingbetween zero and one, a₂ b₁ being equal to 1-a₁ b₁ ; wherein y₁₁ and y₂₁are the said average number of the respective different sequentialrecurring units, y₁₁ being greater than about 20 and less than about 75,y₂₁ being greater than one and less than about 75, n being an averagenumber of total recurring units greater than about 50 and less thanabout 150; and said block polymer being present in said composition inan amount greater than about 7 weight percent.
 65. A composition ofclaim 53, wherein said extended chain polymer includes at least oneblock polymer having the formulas: ##STR1037## wherein a₁ b₁, a₁ b₂ anda₂ b₁ are the said molar proportions of the respective differentrecurring units, a₁ b₁ being between about 0.5 and one, a₁ b₂ or a₂ b₁being equal to 1-a₁ b₁ ; wherein y₁₁ y₁₂ and y₂₁ are the said averagenumber of the respective different sequential recurring units, y₁₁ beinggreater than about 20 and less than about 75, y₁₂ or y₂₁ being greaterthan one and less than about 75, n being an average number of totalrecurring units greater than about 50 and less than about 150; and saidblock polymer being present in said composition in an amount greaterthan about 15 weight percent.
 66. A composition of claim 53, whereinsaid extended chain polymer includes at least one block polymer havingthe formulas: ##STR1038## wherein a₁ b₁, a₁ b₂ and a₂ b₁ are the saidmolar proportions of the respective different recurring units, a₁ b₁being between about 0.6 and one, a₁ b₂ or a₂ b₁ being equal to 1-a₁ b₁ ;wherein y₁₁ and y₁₂ or y₂₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about 30,y₁₂ or y₂₁ being greater than one and less than about 50, n being anaverage number of total recurring units greater than about 50 and lessthan about 150; and said block polymer being present in said compositionin an amount greater than about 15 weight percent.
 67. A composition ofclaim 54, wherein said extended chain polymer includes at least oneblock polymer having the formulas: ##STR1039## wherein c₁ and c₂ are thesaid molar proportions of the respective different recurring units, c₁being between about 0.5 and one, c₂ being equal to 1-c₁ ; wherein y₁ andy₂ are the said average number of the respective different sequentialrecurring units, y₁ being greater than about 30 and less than about 100,y₂ being greater than one and less than about 50, n being an averagenumber of total recurring units greater than about 60 and less thanabout 200; and said block polymer being present in said composition inan amount greater than about 15 weight percent.
 68. A composition ofclaim 55, wherein said extended chain polymer includes at least oneblock polymer having the formula: ##STR1040## wherein a₁ b₁ m/m+m' andc₁ m'/m+m' are the said molar proportions of the respective differentrecurring units, a₁ b₁ m/m+m' being between zero and about 0.5, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than one and less than about 75, y₁ being greater thanabout 30 and less than about 75, n being an average number of totalrecurring units greater than about 75 and less than about 150; and saidblock polymer being present in said composition in an amount greaterthan about 15 weight percent.
 69. A composition of claim 55, whereinsaid extended chain polymer includes at least one block polymer havingthe formula: ##STR1041## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are thesaid molar proportions of the respective different recurring units, a₁b₁ m/m+m' being between about 0.5 and one, c₁ m'/m+m' being equal to1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 30 and less than about 75, y₁ being greater than 5 and less thanabout 30, n being an average number of total recurring units greaterthan about 60 and less than about 150; and said block polymer beingpresent in said composition in an amount greater than about 10 weightpercent.
 70. A composition of claim 55, wherein said extended chainpolymer includes at least one block polymer having the formula:##STR1042## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between zero and 0.5, c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m';wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about oneand less than about 75, y₁ being greater than about 30 and less thanabout 75, n being an average number of total recurring units greaterthan about 75 and less than about 150; and said block polymer beingpresent in said composition in an amount greater than about 15 weightpercent.
 71. A composition of claim 55, wherein said extended chainpolymer includes at least one block polymer having the formula:##STR1043## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between about 0.5 and one, c₁ m'/m+m' being equal to 1-a₁ b₁m/m+m'; wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about 30and less than about 75, y₁ being greater than 5 and less than about 30,n being an average number of total recurring units greater than about 60and less than about 150; and said block polymer being present in saidcomposition in an amount greater than about 10 weight percent.
 72. Acomposition of claim 55, wherein said extended chain polymer includes atleast one block polymer having the formula: ##STR1044## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between zero and 0.5, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than about one and less than about 75, y₁ beinggreater than about 30 and less than about 75, n being an average numberof total recurring units greater than about 75 and less than about 150;and said block polymer being present in said composition in an amountgreater than about 15 weight percent.
 73. A composition of claim 55,wherein said extended chain polymer includes at least one block polymerhaving the formula: ##STR1045## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' arethe said molar proportions of the respective different recurring units,a₁ b₁ m/m+m' being between about 0.5 and one, c₁ m'/m+m' being equal to1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 30 and less than about 75, y₁ being greater than 5 and less thanabout 30, n being an average number of total recurring units greaterthan about 60 and less than about 150; and said block polymer beingpresent in said composition is an amount greater than about 10 weightpercent.
 74. A composition of claim 55, wherein said extended chainpolymer includes at least one block polymer having the formula:##STR1046## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between zero and about 0.5 c₁ m'/m+m' being equal to 1-a₁ b₁m/m+m'; wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about oneand less than about 75, y₁ being greater than about 30 and less thanabout 75, n being an average number of total recurring units greaterthan about 75 and less than about 150; and said block polymer beingpresent in said composition in an amount greater than about 15 weightpercent.
 75. A composition of claim 55, wherein said extended chainpolymer includes at least one block polymer having the formula:##STR1047## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between about 0.5 and one, c₁ m'/m+m' being equal to 1-a₁ b₁m/m+m'; wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about 30and less than about 75, y₁ being greater than 5 and less than about 30,n being an average number of total recurring units greater than about 60and less than about 150; and said block polymer being present in saidcomposition in an amount greater than about 10 weight percent.
 76. Acomposition of claim 55, wherein said extended chain polymer includes atleast one block polymer having the formula: ##STR1048## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between about 0.5 and one,c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are thesaid average number of the respective different sequential recurringunits, y₁₁ being greater than about 30 and less than about 75, y₁ beinggreater than 5 and less than about 30, n being an average number oftotal recurring units greater than about 60 and less than about 150; andsaid block polymer being present in said composition in an amountgreater than about 10 weight percent.
 77. A composition of claim 55,wherein said extended chain polymer includes at least one block polymerhaving the formula: ##STR1049## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' arethe said molar proportions of the respective different recurring units,a₁ b₁ m/m+m' being between about 0.5 and one, c₁ m'/m+m' being equal to1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 30 and less than about 75, y₁ being greater than 5 and less thanabout 30, n being an average number of total recurring units greaterthan about 60 and less than about 150; and said block polymer beingpresent in said composition in an amount greater than about 10 weightpercent.
 78. A composition of claim 55, wherein said extended chainpolymer includes at least one block polymer having the formula:##STR1050## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between about 0.5 and one, c₁ m'/m+m' being equal to 1-a₁ b₁m/m+m'; wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about 30and less than about 75, y₁ being greater than 5 and less than about 30,n being an average number of total recurring units greater than about 60and less than about 150; and said block polymer being present in saidcomposition in an amount greater than about 10 weight percent.
 79. Acomposition of claim 49, wherein said extended chain polymer includes atleast one copolymer selected from the group consisting of recurringunits of the formulas: ##STR1051##
 80. A composition of claim 52,wherein said extended chain polymer includes at least one block polymerhaving the formulas: ##STR1052##
 81. A composition of claim 52, whereinsaid extended chain polymer includes at least one block polymer havingthe formulas: ##STR1053##
 82. A composition of claim 52, wherein saidextended chain polymer includes at least one block polymer having theformulas: ##STR1054##
 83. A composition of claim 52, wherein saidextended chain polymer includes at least one block polymer having theformulas: ##STR1055##
 84. A composition of claim 52, wherein saidextended chain polymer includes at least one block polymer having theformulas: ##STR1056##
 85. A polymer according to claim 2 wherein saidpolymer contains the moiety ##STR1057##
 86. A polymer according to claim2 wherein said polymer contains the moiety ##STR1058##
 87. A polymeraccording to claim 2 wherein said polymer contains the moiety##STR1059##
 88. A polymer according to claim 2 wherein said polymercontains the moiety ##STR1060##
 89. A polymer according to claim 2wherein said polymer contains the moiety ##STR1061##
 90. A compositionaccording to claim 8, wherein said polymer is a formula I extended chainhomopolymer having the formula: ##STR1062##
 91. A composition accordingto claim 90 wherein said polymer has an intrinsic viscosity of fromabout 15 dL/g to about 42 dL/g.
 92. A composition according to claim 8,wherein said polymer is a formula I extended chain homopolymer havingthe formula: ##STR1063##
 93. A composition according to claim 92 whereinsaid polymer has an intrinsic viscosity of from about 9 dL/g to about 24dL/g.
 94. A composition according to claim 7, wherein said polymer is aformula I extended chain homopolymer having the formula: ##STR1064## 95.A composition according to claim 94 wherein said polymer has anintrinsic viscosity of about 15 dL/g.
 96. A composition according toclaim 10, wherein said polymer is a formula II extended chainhomopolymer having the formula: ##STR1065##
 97. a composition accordingto claim 96 wherein said polymer has an intrinsic viscosity of about 12dL/g.
 98. A composition according to claim 10, wherein said polymer is aformula II extended chain homopolymer having the formula: ##STR1066##99. A composition according to claim 90 wherein said polymer has anintrinsic viscosity of about 12 dL/g.
 100. A composition according toclaim 8, wherein said polymer is a formula I extended chain homopolymerhaving the formula: ##STR1067## wherein n is greater than
 60. 101. Acomposition according to claim 1 wherein said polymer contains themoiety ##STR1068##
 102. A composition according to claim 1 wherein saidpolymer contains the moiety ##STR1069##
 103. A composition according toclaim 1 or 2 wherein said polymer contains the moiety ##STR1070##
 104. Acomposition according to claim 1 or 2 wherein said polymer contains themoiety ##STR1071##
 105. A composition according to claim 1 or 2 whereinsaid polymer contains the moiety ##STR1072##
 106. A compositionaccording to claim 1 or 2 wherein said polymer contains the moiety##STR1073##
 107. A composition according to claim 1 or 2 wherein saidpolymer contains the moiety ##STR1074##
 108. A composition according toclaim 1 or 2 wherein said polymer contains the moiety ##STR1075##
 109. Acomposition according to claim 1 or 2 wherein said polymer contains themoiety ##STR1076##
 110. A composition according to claim 1 wherein saidpolymer contains the moiety ##STR1077##
 111. A composition according toclaim 1 or 2 wherein said polymer contains the moiety ##STR1078##
 112. Acomposition according to claim 1 wherein said polymer contains themoiety ##STR1079##
 113. A composition according to claim 1 or 2 whereinsaid polymer contains the moiety ##STR1080##
 114. A compositionaccording to claim 1 or 2 wherein said polymer contains the moiety##STR1081##
 115. A composition according to claim 1 or 2 wherein saidpolymer is a formula II extended chain homopolymer having the formula:##STR1082##
 116. A composition according to claim 11 wherein saidpolymer has an intrinsic viscosity of about 5 dL/g.
 117. A compositionaccording to claim 115 wherein said polymer has an intrinsic viscosityof about 7 dL/g.
 118. A composition according to claim 7, wherein saidorganic group is phenyl, pyridyl, or methyl.
 119. A compositionaccording to claim 34, wherein said organic group is phenyl, pyridyl, ormethyl.
 120. A composition according to claim 52, wherein said organicgroup is phenyl, pyridyl, or methyl.
 121. A composition according toclaim 8, wherein said polymer is a formula I extended chain homopolymerhaving the formula: ##STR1083## wherein n is greater than 60.